CN101365587B - Multilayer body - Google Patents

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Publication number
CN101365587B
CN101365587B CN2007800017034A CN200780001703A CN101365587B CN 101365587 B CN101365587 B CN 101365587B CN 2007800017034 A CN2007800017034 A CN 2007800017034A CN 200780001703 A CN200780001703 A CN 200780001703A CN 101365587 B CN101365587 B CN 101365587B
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expression
formula
composition
repetitive
mole
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CN101365587A (en
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喜田稔男
梶原俊典
新见亮
菅武宏
浴中达矢
高冈伸彰
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Teijin Ltd
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Teijin Chemicals Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
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  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

Disclosed is a multilayer body comprising a base, a first layer obtained by thermally curing an acrylic resin composition, and a second layer obtained by thermally curing an organosiloxane resin composition. This multilayer body is excellent in weather resistance, wear resistance and the like. The first layer mainly contains an acrylic copolymer containing 1-85 mol% of a cycloalkyl group-containing unit, a block polyisocyanate compound, a curing catalyst and a triazine ultraviolet absorbent. The second layer is composed of a colloidal silica and a hydrolysis-condensation product of an alkoxysilane.

Description

Duplexer
Technical field
The present invention relates to a kind of duplexer, further particularly, relate to a kind of duplexer that on base material, stacks gradually acrylate resin layer (ground floor) and organosiloxane resins composition (second layer) with excellent weatherability.
Background technology
The speciality of its resistance to impact of plastic material performance, light weight, processability etc. can be used in the multiple use.Particularly, as the acrylic resin of transparent plastic, polycarbonate resin, styrene resin etc., can be used as substitute and the extensive use of glass.But the weatherability of known these resins is insufficient, in long outdoor application, causes decomposition/deterioration, thereby damages its physical property, outward appearance.And the mar proof of these resins is also poor, and the surface is damaged easily, also has easily by the shortcoming of nip.
In recent years, performance its light weight, security being arranged and particularly be suitable for the transparent plastic in the automobile window glass at glass pane is the trend of the lucite of base material.In this lucite, require the weatherability of the height of its degree with glass.In addition, in front in the glass, must prevent the scratch that causes because of the wiper action, and in side window, then must prevent the scratch going up and down to cause because of window glass, dimension requires to have excellent mar proof.
For weatherability and the mar proof that improves lucite, proposed much to use the scheme of organosiloxane resins layer before this at substrate surface.For example, in patent documentation 1 and 2, a kind of partial condensate of ortho-siliformic acid and resin combination of cataloid of containing disclosed.Further, in patent documentation 3 and 4, a kind of resin combination that in the condensation product of alkyltrialkoxysilaneand and tetraalkoxysilane, has added cataloid is disclosed.
But; Though the curing tunicle of these resin combinations has mar proof to a certain degree,, solidify tunicle and be stretched owing to the difference of base material under hot environment with the thermal coefficient of expansion that solidifies tunicle; Thereby in solidifying tunicle, crack sometimes, thereby the problem of durability is arranged.
In order to improve this defective, proposed between base material and organosiloxane resins layer, the method for Thermocurable acrylate resin layer to be set.For example, in patent documentation 5, proposed to use the method for the acrylic acid-urethane resin layer that obtains by the how pure and mild isocyanate compound of acrylic acid as the Thermocurable acrylic resin.But because isocyanate compound is reactive high, the storage stability of coating composition is low, and in use or in preservation, viscosity increases easily and is prone to solation.And, also have the shortcoming that when heat cure, is easy to generate side reaction.
In patent documentation 6 or 7, proposed to adopt the method for the ethene copolymer that contains alkoxysilyl as the Thermocurable acrylic resin.But, owing to slowly reacting, the moisture in alkoxysilyl and the composition causes hydrolyzing, therefore, exist the viscosity increased of composition or produce the problem of solation.
In addition, in patent documentation 8, disclosing with (methyl) acrylic acid alkyl-cyclohexyl Arrcostab is the resin combination of necessary composition.The weatherability of this resin combination is insufficient and the leeway of improvement is arranged.
On the other hand, in order to improve weatherability, the known method that interpolation ultra-violet absorber in the Thermocurable acrylate resin layer is arranged.For example, in patent documentation 9, proposed in the Thermocurable acrylic resin to add the ultra-violet absorber of benzotriazole and the method for improving weatherability.But,, in long-time the use, suppress the light deterioration degree limited in one's ability of base material because of the light decomposition rate of ultra-violet absorber self is very big.In addition, when strengthening the addition of ultra-violet absorber in order to improve this shortcoming, the connecting airtight property reduction between base material or the organosiloxane resins layer.
In addition, as the little ultra-violet absorber of light decomposition rate, known have a triazines ultra-violet absorber.But, when being added on the triazines ultra-violet absorber in the Thermocurable acrylic resin, cause the albefaction of solidifying tunicle easily because of exposing to the open air outdoor, be easy to deface or transparent shortcoming and have.
Patent documentation 1:JP spy opens clear 51-002736 communique
Patent documentation 2:JP spy opens clear 55-094971 communique
Patent documentation 3:JP spy opens clear 63-278979 communique
Patent documentation 4:JP spy opens flat 01-306476 communique
Patent documentation 5:JP spy opens clear 62-169832 communique
Patent documentation 6:JP spy opens clear 59-109528 communique
Patent documentation 7:JP spy opens the 2004-131549 communique
Patent documentation 8:JP spy opens the 2002-206042 communique
Patent documentation 9:JP spy opens the 2000-318106 communique
Summary of the invention
The object of the present invention is to provide the duplexer of a kind of weatherability, excellent in wear resistance.The object of the present invention is to provide the excellent duplexer of connecting airtight property.
The inventor etc. are directed to the duplexer of the second layer that on base material, is formed with the ground floor that is made up of acrylic resin successively and is made up of organosiloxane resins, have inquired into the problem that improves weatherability.Consequently; Find when ground floor contain the little triazines ultra-violet absorber of light decomposition rate and contain polarity low have the acrylate copolymer of cyclohexyl the time; The dispersiveness of ultra-violet absorber improves; And can protect the active site of ultra-violet absorber, can continue to bring into play the effect of ultra-violet absorber, the duplexer that can obtain having excellent weather resistance.
In addition, found when ground floor comprises the acrylate copolymer with urethane bonds, can obtain the excellent duplexer of connecting airtight property, particularly the connecting airtight property under hot environment.The present invention promptly is based on above-mentioned opinion and draws.
Promptly; The present invention provides a kind of duplexer; This duplexer has base material, acrylic acid resin composition is carried out ground floor that heat cure forms and the organosiloxane resins composition is carried out the second layer that heat cure forms; And the order according to base material, ground floor and the second layer forms, and it is characterized in that
Said acrylic acid resin composition comprises: (A) acrylic copolymer, and it contains the repetitive with following formula (A) expression of at least 70 moles of %; (B) block polyisocyanate compound, it has the ratio that is converted into NCO of 5.5～50 weight %, and with respect to the hydroxyl in the acrylic copolymer of the formula (A) of 1 equivalent, has the NCO of 0.8～1.5 equivalent; (C) curing catalysts, it is 0.001～0.4 weight portion with respect to (A) composition of 100 weight portions and (B) total amount of composition; And (D) triazines ultra-violet absorber; Its with respect to (A) composition of 100 weight portions and (B) total amount of composition be 0～40 weight portion; And with following formula (D) expression, and the triazines ultra-violet absorber residue in the formula (A) is 1～40 weight % with (D) total content of composition;
In the formula; X is hydrogen atom or methyl; Y is that methyl, ethyl, cycloalkyl, carbon number are 2～5 hydroxy alkyl or triazines ultra-violet absorber residue; And the ratio of hydrogen atom is 30 moles below the % in X, and the ratio of cycloalkyl is that the ratio of 1～85 mole of %, triazines ultra-violet absorber residue is that the ratio of 0～15 mole of %, ethyl is 1～98 mole of % among the Y;
Figure S2007800017034D00041
In the formula, R 4The expression carbon number is 1～18 alkyl, with-CH 2CH (OH) CH 2O-R 8Substituting group (wherein, the R of expression 8Be that carbon number is 1～18 alkyl) or with-CH (CH 3) C (O) O-R 9Substituting group (wherein, the R of expression 9Be that carbon number is 1～18 alkyl), R 5Expression hydrogen atom, carbon number are that 1～18 alkyl or carbon number are 1～18 alkoxyl, R 6, R 7Represent independently that respectively hydrogen atom, carbon number are that 1～18 alkyl, carbon number are 1～18 alkoxyl or can are 1～18 alkyl or the substituted phenyl of halogen atom by carbon number that V representes that hydrogen atom, OH base or carbon number are 1～12 alkyl;
Said organosiloxane resins composition comprises: (E) cataloid; (F) hydrolytic condensate of alkoxy silane, it is represented with following formula (F); And (G) metal oxide, and (E) content of composition is 10～60 weight %, (F) content of composition is converted into R 1 mR 2 nSiO (4-m-n)/2Be 40～90 weight %, with respect to (E) composition of 100 weight portions and (F) total amount of composition, (G) composition is 0～15 weight portion,
R 1 mR 2 nSi(OR 3) 4-m-n (F)
In the formula, R 1, R 2Represent independently that respectively carbon number is 1～4 alkyl, vinyl or selected free methyl acryloxy, amino, glycidoxy and 3, a substituted carbon number of above group in the group that the 4-epoxycyclohexyl is formed is 1～3 alkyl, R 3Be the alkyl or the vinyl of carbon number 1～4, m, n represent the arbitrary integer in 0,1,2 respectively independently, and m+n is the arbitrary integer in 0,1,2.
The present invention includes the glass pane that forms by this duplexer.
The present invention provides a kind of acrylic acid resin composition, it is characterized in that, comprising:
(A) acrylic copolymer; It contains the repetitive of representing with following formula (A-4) of the repetitive of representing with following formula (A-3) and 0～15 mole of % of the repetitive with following formula (A-2) expression of the repetitive with following formula (A-1) expression of 1～98 mole of %, 1～85 mole of %, 1～15 mole of %, and their total amount is at least 70 moles of %; (B) block polyisocyanate compound, it has the ratio that is converted into NCO of 5.5～50 weight %, and with respect to the hydroxyl in the acrylic copolymer of 1 equivalent, has the NCO of 0.8～1.5 equivalent; (C) curing catalysts, it is 0.001～0.4 weight portion with respect to (A) composition of 100 weight portions and (B) total amount of composition; And (D) triazines ultra-violet absorber; Its with respect to (A) composition of 100 weight portions and (B) total amount of composition be 0～40 weight portion, and with following formula (D) expression, and; Triazines ultra-violet absorber residue in the formula (A-4) is 1～40 weight % with (D) total content of composition
In the formula, Y 1Be methyl or ethyl, Y 2Be cycloalkyl, X 1Be hydrogen atom or methyl, X 2Be hydrogen atom or methyl, Y 3Be the alkylidene of carbon number 2～5, Y 4Be triazines ultra-violet absorber residue, X 3Be hydrogen atom or methyl.
In addition; The present invention provides a kind of organosiloxane resins composition; It is characterized in that (E) cataloid, (F) be with the hydrolytic condensate of the alkoxy silane of following formula (F) expression and (G) metal oxide dissolving and/or be dispersed in the solvent, and (i) be converted into R when weight (F) composition 1 mR 2 nSiO (4-m-n)/2Weight the time; At 100 weight % (E) composition and (F) in the total amount of composition; (E) content of composition is that the content of 10～60 weight %, (F) composition is 40～90 weight %, and reaches (F) total amount of composition with respect to (E) composition of 100 weight portions, and (G) content of composition is 0.1～15 weight portion; (ii) in the laser diffractometry particle size distribution, with accumulation 50% particle diameter of (G) composition and when accumulating 90% particle diameter respectively as D50 and D90, D90 is below the 100nm, and D90/D50 is below 20,
R 1 mR 2 nSi(OR 3) 4-m-n (F)
In the formula, R 1, R 2Represent independently that respectively carbon number is 1～4 alkyl, vinyl or selected free methyl acryloxy, amino, glycidoxy and 3, a substituted carbon number of above group in the group that the 4-epoxycyclohexyl is formed is 1～3 alkyl, R 3Be the alkyl or the vinyl of carbon number 1～4, m, n represent the arbitrary integer in 0,1,2 respectively independently, and m+n is the arbitrary integer in 0,1,2.
The specific embodiment
< acrylic acid resin composition >
Acrylic acid resin composition of the present invention contains (A) acrylic copolymer, (B) block polyisocyanate compound, (C) curing catalysts and (D) triazines ultra-violet absorber.Below, (A)～(D) composition is carried out detailed explanation.
(acrylic copolymer (A))
Acrylic copolymer (below, be called " A " composition sometimes) is the acrylic copolymer with the repetitive of following formula (A) expression that contains at least 70 moles of %.
Figure S2007800017034D00061
In the formula, X is hydrogen atom or methyl.In X, the ratio of hydrogen atom is 30 moles below the %.
Y is the hydroxy alkyl or the triazines ultra-violet absorber residue of methyl, ethyl, cycloalkyl, carbon number 2～5.In Y, the ratio of cycloalkyl is 1～85 mole of %, and the ratio of triazines ultra-violet absorber residue is 0～15 mole of %, and the ratio of ethyl is 1～98 mole of %.
The repetitive that preferred acrylic copolymer contains useful following formula (A-1), (A-2), (A-3) and (A-4) representes.
((A-1) unit)
Figure S2007800017034D00071
In the formula (A-1), Y 1Be methyl or ethyl.With the repetitive of formula (A-1) expression, obtain by polymerization methyl methacrylate, EMA.These both can use separately, also can mix both and use.
The content of the formula in the acrylic copolymer (A-1) unit is preferably 1～98 mole of %.When the ratio of (A-1) unit was less than 1 mole of %, the flexible reduction of ground floor was prone in the second layer crack.And, and the connecting airtight property reduction between the base material or the second layer, thereby not preferred.
((A-2) unit)
Figure S2007800017034D00072
In the formula (A-2), X 1Be hydrogen atom or methyl, Y 2Be cycloalkyl.With the repetitive of formula (A-2) expression, obtain by the acrylic acid ester that contains a cycloalkyl in the polymerizable molecular at least or methacrylate.The carbon number of preferred cycloalkyl is 5～12.Particularly, can enumerate cyclohexyl, ring octyl group etc.
With the repetitive of (A-2) expression, can be through pairing monomer copolymerizable be imported.Object lesson as the monomer of correspondence; Can enumerate cyclohexyl acrylate, acrylic acid 4-methylcyclohexyl ester, acrylic acid 2; 4-Dimethylcyclohexyl ester, acrylic acid 2; 4,6-trimethylcyclohexyl, acrylic acid 4-tert-butylcyclohexyl ester, acrylic acid adamantane esters, acrylic acid DCPA, acrylic acid cyclohexyl methyl esters, acrylic acid 4-methylcyclohexyl methyl esters, acrylic acid 2,4-Dimethylcyclohexyl methyl esters, acrylic acid 2; 4; 6-trimethylcyclohexyl methyl esters, acrylic acid 4-tert-butylcyclohexyl methyl esters, methacrylic acid cyclohexyl ester, methacrylic acid 4-methylcyclohexyl ester, methacrylic acid 2,4-Dimethylcyclohexyl ester, methacrylic acid 2,4; 6-trimethylcyclohexyl, methacrylic acid 4-tert-butylcyclohexyl ester, methacrylic acid adamantane esters, methacrylic acid DCPA, methacrylic acid cyclohexyl methyl esters, methacrylic acid 4-methylcyclohexyl methyl esters, methacrylic acid 2; 4-Dimethylcyclohexyl methyl esters, methacrylic acid 2,4, compounds such as 6-trimethylcyclohexyl methyl esters, methacrylic acid 4-tert-butylcyclohexyl methyl esters.These compounds both can use separately, also can two or more mixing use.Wherein, preferably adopt cyclohexyl methacrylate.
The content of (A-2) unit in the acrylic copolymer is preferably 1～85 mole of %.When the ratio of (A-2) unit was lower than 1 mole of %, the dispersiveness of triazines ultra-violet absorber reduced, and albefaction appears in ground floor easily, when surpassing 85 moles of %, with the connecting airtight property reduction of the base material or the second layer.
((A-3) unit)
Figure S2007800017034D00081
In the formula (A-3), X 2Be hydrogen atom or methyl, Y 3Alkylidene for carbon number 2～5.As alkylidene, can enumerate vinyl, trimethylene, tetramethylene etc.(A-3) unit is characterised in that and has hydroxyl.
(A-3) unit can be through importing pairing monomer copolymerizable.As the object lesson of the monomer of correspondence, can enumerate 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, acrylic acid-2-hydroxy propyl ester, methacrylic acid-2-hydroxy propyl ester, acrylic acid-3-hydroxy propyl ester, methacrylic acid-3-hydroxy propyl ester, acrylic acid-4-hydroxyl butyl ester, methacrylic acid-4-hydroxyl butyl ester, acrylic acid-3-hydroxyl butyl ester, methacrylic acid-3-hydroxyl butyl ester, acrylic acid-2-hydroxyl butyl ester, methacrylic acid-2-hydroxyl butyl ester etc.These both can use separately, also can mix two or more uses.Wherein, preferable methyl 2-Hydroxy ethyl acrylate.
The content of (A-3) unit in the acrylic copolymer is preferably 1～15 mole of %, more preferably 5～15 moles of %.When the ratio of (A-3) unit surpasses above-mentioned scope, be coated with and be easy to generate crackle in the rete, thereby not preferred.
((A-4) unit)
Figure S2007800017034D00082
In the formula (A-4), X 3Be hydrogen atom or methyl, Y 4Be triazines ultra-violet absorber residue.
(A-4) unit can import through the acrylic acid ester or the methacrylate monomer combined polymerization that will have triazines ultra-violet absorber residue.As acrylic acid ester or methacrylate monomer, can enumerate 2-[4-(2-acryloxy-3-dodecyloxy propyl group) oxygen]-2-hydroxy phenyl particularly with triazines ultra-violet absorber residue]-4,6-two (2, the 4-3,5-dimethylphenyl)-1; 3,5-triazine, 2-[4-(2-acryloxy-3-tridecane oxygen base propyl group) oxygen]-2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1; 3,5-triazine, 2-[4-(2-acryloxy-3-(2-ethyl hexyl oxy) propyl group) oxygen]-2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1; 3,5-triazine, 2-[4-(2-methacryloxy-3-dodecyloxy propyl group) oxygen]-2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1; 3,5-triazine, 2-[4-(2-methacryloxy-3-tridecane oxygen base propyl group) oxygen]-2-hydroxy phenyl]-4,6-two (2; The 4-3,5-dimethylphenyl)-and 1,3,5-triazines, 2-[4-(2-acryloxy-3-(2-ethyl hexyl oxy) propyl group) oxygen]-2-hydroxy phenyl]-4; 6-two (2, the 4-3,5-dimethylphenyl)-1,3; 5-triazine, 2-[4-(2-methacryloxy-3-(2-ethyl hexyl oxy) propyl group) oxygen]-2-hydroxy phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1; 3,5-triazine, 2-[4-(2-hydroxyl-3-(2-ethyl hexyl oxy) propyl group) oxygen]-2-hydroxy phenyl]-4,6-two (2; The 4-3,5-dimethylphenyl)-the addition reaction product of 1,3,5-triazines and 2-isocyanates ethyl acrylate; 2-[4-(2-hydroxyl-3-(2-ethyl hexyl oxy) propyl group) oxygen]-2-hydroxy phenyl]-4, the addition reaction product of 6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines and 2-isocyanates EMA etc.These both can use separately, also can two or more mixing use.Wherein, preferably adopt 2-[4-(2-hydroxyl-3-(2-ethyl hexyl oxy) propyl group) oxygen]-2-hydroxy phenyl]-4,6-two (2; The 4-3,5-dimethylphenyl)-and addition reaction product, the 2-[4-(2-methacryloxy-3-(2-ethyl hexyl oxy) propyl group) oxygen]-2-hydroxy phenyl of 1,3,5-triazines and 2-isocyanates EMA]-4; 6-two (2; The 4-3,5-dimethylphenyl)-1,3,5-triazines.
Particularly, the preferred use by acrylic monomers repeat units derived with following formula (A-4-a) or formula (A-4-b) expression.
Figure S2007800017034D00101
(in the formula, R 11Be the alkylidene of carbon number 2～6, R 12Expression hydrogen atom, the alkyl of carbon number 1～18 or the alkoxyl of carbon number 1～18, R 13, R 14Identical or represent independently of each other hydrogen atom, halogen atom, carbon number 1～18 alkyl, carbon number 1～18 alkoxyl or can be by the alkyl of carbon number 1～18 or the substituted phenyl of halogen atom, R 15The alkyl of expression carbon number 1～18, X 4Be hydrogen atom or methyl, V 1The alkyl of expression hydrogen atom, OH base or carbon number 1～12.)
(in the formula, R 16Expression hydrogen atom, the alkyl of carbon number 1～18 or the alkoxyl of carbon number 1～18, R 17, R 18Identical or represent independently of each other hydrogen atom, halogen atom, carbon number 1～18 alkyl, carbon number 1～18 alkoxyl or can be by the alkyl of carbon number 1～18 or the substituted phenyl of halogen atom, R 19The alkyl of expression carbon number 1～18, X 5Be hydrogen atom or methyl, V 2The alkyl of expression hydrogen atom, OH base or carbon number 1～12.)
In the present invention, triazines ultra-violet absorber residue is the residue of triazines ultra-violet absorber and have the ultraviolet radiation absorption function.Triazines ultra-violet absorber residue, because the terminal part of its triaizine compounds comes off and combines with acrylic copolymer, therefore, the molecular weight of residue and triaizine compounds is different strictly speaking.But the weight of the part that comes off is very small than integral body, therefore, for ease in the present invention, supposes that the weight of weight and triaizine compounds of residue is identical.
The content of (A-4) unit in the acrylic copolymer is preferably 0～15 mole of %, and more preferably 0～10 mole of % further is preferably 0～7 mole of %.When the ratio of (A-4) unit surpassed 15 moles of %, crackle appearred in the connecting airtight property reduction of base material and ground floor, ground floor and the second layer easily in the second layer.
Triazines ultra-violet absorber residue in the formula (A-4) is preferably 1～40 weight % with (D) total content of composition, more preferably 2～30 weight %.
The total content of the repetitive of usefulness formula (A-1)～(A-4) expression in the acrylic copolymer is at least 70 moles of %, is preferably 80～100 moles of %, more preferably 90～100 moles of %.
The unit of formula (A-4) of unit and 0～15 mole of % that preferably contains the formula (A-3) of the unit of the formula (A-2) of the unit of the formula (A-1) of 1～98 mole of %, 1～85 mole of %, 1～15 mole of % in the acrylic copolymer.
Acrylic copolymer; Balance according to the performance of the low volatilization of its weatherability, mar proof, connecting airtight property, hot water resistance, ultra-violet absorber or stripping property etc.; The preferred composition that adopts acrylic copolymer [I] and acrylic copolymer (II); Wherein, Acrylic copolymer [I] has been given prominence to connecting airtight property especially, and ultra-violet absorber was from the performances such as stripping of ground floor to the organosiloxane resins composition when acrylic copolymer (II) had been given prominence to the volatilization of the ultra-violet absorber when acrylic acid resin composition is heating and curing or suppressed the formation second layer.
In the acrylic copolymer [I], the total content of the repetitive of the repetitive of the repetitive of formula (A-2) expression of the repetitive of the formula of 50～98 moles of % (A-1) expression, 1～35 mole of %, formula (A-3) expression of 1～15 mole of % and formula (A-4) expression of 0～10 mole of % is at least 70 moles of %.
In the acrylic copolymer [II], the total content of the repetitive of the repetitive of formula (A-3) expression of the repetitive of the formula of 1～60 mole of % (A-1) expression, the repetitive that surpasses formula (A-2) expression below 35 moles of % and the 85 moles of %, 1～15 mole of % and formula (A-4) expression of 0.1～15 mole of % is at least 70 moles of %.
The content of the repetitive of usefulness formula (A-4) expression of preferred acrylic copolymer is 0 mole of %, and with respect to (A) composition of 100 weight portions and (B) total amount of composition, (D) content of composition is 1～40 weight portion.
And preferably with respect to (A) composition of 100 weight portions and (B) total amount of composition, (D) content of composition is 0 weight portion, and the content of the repetitive of usefulness formula (A-4) expression of acrylic copolymer is 0.1～15 mole of %.
((A-5) unit)
Preferred acrylic copolymer advances-goes on foot to contain the repetitive of useful following formula (A-5) expression.Through containing (A-5) unit, can improve weatherability.
Figure S2007800017034D00121
In the formula, R 10The alkyl or the alkoxyl of expression hydrogen atom, carbon number 1～14.
R 10Be preferably the alkyl or the alkoxyl of carbon number 1～8.Particularly, can enumerate methyl, ethyl, propyl group, butyl, methoxyl group, ethyoxyl, propoxyl group, butoxy etc.
In the repetitive total amount with respect to the acrylic copolymer of 100 moles of %, the ratio of preferred (A-5) unit is 0.1～15 mole of %, and more preferably 0.1～10 mole of % further is preferably 1～8 mole of %.When surpassing 15 moles of %, reduce easily with the connecting airtight property of the base material or the second layer.
Preferably in acrylic copolymer [I]; The unit of formula (A-5) of unit and 0.1～10 mole of % that contains the formula (A-4) of the unit of the formula (A-3) of the unit of the formula (A-2) of the unit of the formula (A-1) of 50～97.9 moles of %, 1～35 mole of %, 1～15 mole of %, 0～10 mole of %; And; In the repetitive total amount of the acrylic copolymer of 100 moles of %, (A-1)～(A-5) total content of unit is at least 70 moles of %.
Preferably in acrylic copolymer [II]; The unit of formula (A-5) of unit and 0.1～20 mole of % that contains the formula (A-4) of the unit of the formula (A-3) of the unit of the formula (A-1) of 1～59.9 mole of %, the unit that surpasses the formula (A-2) below 35 moles of % and the 85 moles of %, 1～15 mole of %, 0.1～10 mole of %; And; In the repetitive total amount of the acrylic copolymer of 100 moles of %, (A-1)～(A-5) total content of unit is at least 70 moles of %.
Through containing (A-5) unit, can give the radical-scavenging ability, and can further improve weatherability.In the repetitive total amount of the acrylic copolymer of 100 moles of %, the total content of preferred (A-1)～(A-5) unit is at least 70 moles of %, and more preferably at least 80 moles of % further are preferably at least 90 moles of %.
(A-5) unit can import through pairing acrylic acid ester of combined polymerization and/or methacrylate monomer.As the monomer of correspondence, can enumerate methacrylic acid 2,2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1,2; 2,6,6-pentamethyl-4-piperidines ester, methacrylic acid 1-ethyl-2,2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-propyl group-2; 2,6,6-tetramethyl-4-piperidines ester, the methacrylic acid 1-tert-butyl group-2,2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-cyclohexyl-2; 2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-(4-methylcyclohexyl)-2,2,6,6-tetramethyl-4-piperidines ester, methacrylic acid uncle 1-octyl group-2; 2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-decyl-2,2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-dodecyl-2; 2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-methoxyl group-2,2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-ethyoxyl-2; 2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-propoxyl group-2,2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-tert-butoxy-2; 2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-(4-methyl cyclohexane oxygen base)-2; 2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-octyloxy-2,2,6,6-tetramethyl-4-piperidines ester, methacrylic acid uncle 1-octyloxy-2; 2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-oxygen in last of the ten Heavenly stems base-2,2,6,6-tetramethyl-4-piperidines ester, methacrylic acid 1-dodecyloxy-2; 2,6,6-tetramethyl-4-piperidines ester etc., these both can use separately, can also two or more combinations use.
(other unit)
Functional etc. in order further to give, the acrylic copolymer ((A) composition) that contains (A-1)～(A-5) unit can also contain other repetitive.With respect to the repetitive total amount of the acrylic copolymer of (A) composition of 100 moles of %, other repetitives are 30 moles below the %, are preferably 20 moles below the %, are preferably 10 moles especially below the %.
Other repetitive can import through copolymerization of ethylene class monomer, this vinyl monomer can with acrylic acid ester or methacrylate monomer combined polymerization.As other vinyl monomer; Consider from the durability aspect of adherence or weatherability etc.; Can enumerate acrylic acid, methacrylic acid, acrylic acid amides, methacrylic acid acid amides, methyl acrylate, ethyl acrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid 2-ethylhexyl, dodecylacrylate, lauryl methacrylate, 2-(2 '-hydroxyl-5 '-acryloxy ethylphenyl) BTA, 2-(2 '-hydroxyl-5 '-acryloxy ethoxyl phenenyl) BTA, 2-(2 '-hydroxyl-5 '-acryloxy propyl group phenyl) BTA, 2-(2 '-hydroxyl-5 '-acryloxy propoxyl group phenyl) BTA, 2-(2 '-hydroxyl-5 '-acryloxy ethylphenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 '-acryloxy ethyl-5 '-tert-butyl-phenyl) BTA, 2-(2 '-hydroxyl-3 '-acryloxy ethyl-5 '-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-hydroxyl-4-(acryloyl-oxy base oxethyl) benzophenone, 2-hydroxyl-4-(acryloxy propoxyl group) benzophenone, 2; 2 '-dihydroxy-4-(acryloyl-oxy base oxethyl) benzophenone, 2-hydroxyl-4-(acryloxy ethyl) benzophenone, 2-(2 '-hydroxyl-5 '-methacryloxyethyl phenyl) BTA, 2-(2 '-hydroxyl-5 '-methacryloxy ethoxyl phenenyl) BTA, 2-(2 '-hydroxyl-5 '-methacryloxypropyl phenyl) BTA, 2-(2 '-hydroxyl-5 '-methacryloxy propoxyl group phenyl) BTA, 2-(2 '-hydroxyl-5 '-methacryloxyethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 '-methacryloxyethyl-5 '-tert-butyl-phenyl) BTA, 2-(2 '-hydroxyl-3 '-methacryloxyethyl-5 '-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-hydroxyl-4-(methacryloxy ethyoxyl) benzophenone, 2-hydroxyl-4-(methacryloxy propoxyl group) benzophenone, 2; 2 '-dihydroxy-4-(methacryloxy ethyoxyl) benzophenone, 2-hydroxyl-4-(methacryloxyethyl) benzophenone etc.; These both can use separately, also can two or more mixing use.In addition, acrylic resin need not to use separately the resin of single composition, can also acrylic resin mixed two or more and uses.
(A) molecular weight of the acrylic copolymer of composition is represented with weight average molecular weight, is preferably more than 20,000, more preferably more than 50,000.In addition, preferably using weight average molecular weight is the acrylic copolymer below 1,000 ten thousand.Therefore, the weight average molecular weight of acrylic copolymer is preferably 50,000～1,000 ten thousand, more preferably 50,000～1,000,000, further is preferably 50,000～500,000.When the molecular weight of acrylic copolymer during in this scope, can give full play to performance as the connecting airtight property of ground floor or intensity etc., thereby preferred.
(block polyisocyanate compound (B))
(B) composition is with NCO and block agent reaction, eliminates nearly all free NCO, thereby does not have reactivity, and can make block agent separation become NCO through heating, thereby have reactive compound.
As (B) composition, the following block agent of can having enumerated on the NCO of polyisocyanate compounds addition and the block isocyanate compound that obtains, said block agent is with oximes such as acetoxime, methyl ethyl ketoximes; Malonic acid dimethyl esters, malonic acid diethyl ester, methyl acetoacetate, ethyl acetoacetate, acetylacetone,2,4-pentanedione isoreactivity methylene compound; Methyl alcohol, ethanol, 2-propyl alcohol, n-butanol, sec-butyl alcohol, 2-ethyl-alcohols such as 1-hexanol; Phenol such as phenol, cresols, ethyl-phenol are the block agent of representative.
As the polyisocyanate compounds of addition block agent, each other cyclopolymer of the addition product, PIC that can enumerate PIC, PIC and polyalcohol, isocyanates biuret body etc.As PIC, can enumerate toluene di-isocyanate(TDI), 4; 4-methyl diphenylene diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine vulcabond, XDI, LDI, trimethyl hexamethylene diisocyanate, dimeric dibasic acid (Dimeric acid) vulcabond, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, IPDI etc.
(B) composition; When heat cure is reacted, begin just to generate NCO, therefore, the storage stability of its coating composition is excellent; And; Consumption with coating composition in or airborne moisture, be used for the NCO in the side reaction of alcohols solvent of solvent coated composition amount few, be difficult to be coated with the influence of environment, can form curing tunicle with stable physical property.This blocked isocyanate both can use separately, also can mix two or more uses.
In blocked isocyanate, the weatherability of block aliphatic and/or alicyclic polymeric isocyanate compound is excellent especially, thereby preferred.As block aliphatic and/or alicyclic polymeric isocyanate compound; Preferably (i) with the additive poly isocyanate compound of additive poly isocyanate compound with block agent blockization, and hydroxy compounds that this additive poly isocyanate compound can be through will having 2～4 hydroxyls and aliphatic and/or ester ring type diisocyanate cpd react and obtain; (ii) with the isocyanuric acid ester type polyisocyanate compounds of isocyanuric acid ester type polyisocyanate compounds with block agent blockization, this isocyanuric acid ester type polyisocyanate compounds is derived by aliphatic and/or ester ring type diisocyanate cpd.Wherein, the carbon number of aliphatic diisocyanate cpd and/or alicyclic diisocyanate compound is 4～20, and more preferably carbon number is 4～15.Carbon number through making isocyanate compound can form filming of excellent in te pins of durability in this scope.
What be converted into that the ratio of NCO representes is, has separated under the situation of block agent when heating (B) composition, and the weight of the NCO that is generated is with respect to the percentage of the weight of (B) composition.
(B) ratio that is converted into NCO of composition is 5.5～50 weight %, is preferably 6.0～40 weight %, most preferably is 6.5～30 weight %.When the ratio that is converted into NCO is lower than 5.5 weight %, increase with respect to the use level of the block polyisocyanate compound of acrylic resin, with the connecting airtight property shortcoming of base material.In addition, when the ratio that is converted into NCO surpasses 50 weight %, be coated with the flexible reduction of rete, when the heat cure second layer, be coated with rete and crack, impaired to the durability of environmental change.Be converted into the ratio (weight %) of NCO, NCO carry out ureaization, the method that excessive amine carries out titration is obtained with acid through amine with known quantity.
(B) content of composition does, with respect to the hydroxyl in the acrylic copolymer (A) of 1 equivalent, NCO is 0.8～1.5 equivalent, is preferably 0.8～1.3 equivalent, most preferably is 0.9～1.2 equivalent.
(A) hydroxyl in the composition and NCO in (B) composition form crosslinkedly through urethane bonds, can make good the connecting airtight property of ground floor maintenance and base material and the second layer thus.In addition, be difficult to produce the reduction phenomenon of the crosslink density that causes because of ultraviolet ray, water, oxygen etc., can keep connecting airtight property for a long time.And, can also keep the durability under the hot environment.Further, weatherability is also excellent.
If NCO is lower than 0.8 equivalent, because crosslinked insufficient, therefore the durability under hot environment becomes insufficient, and, because unreacted hydroxyl and hydrone demonstrate high compatibility, therefore, producing hygroscopic effect, weatherability or hear resistance are also poor.When NCO surpassed 1.5 equivalents, ground floor became the very high not only hard but also crisp layer of crosslink density that is accompanied by the allophanic acid ester bond, to the bad adaptability of environmental change, owing to environmental change causes connecting airtight property poor.
(curing catalysts (C))
(C) composition is a curing catalysts.Curing catalysts is to use for the disassociation of the block agent that promotes (B composition).And, react for the urethane esterification between the hydroxyl in the NCO that promotes to generate and (A) composition and to use through disassociation.
As (C) composition, be preferably selected from least a compound in the group of forming by organo-tin compound, organic titanic compound, organic zirconate, tertiary amine compound, quarternary ammonium salt compound.
In these curing catalysts, preferably adopt organo-tin compound, the preferred especially organo-tin compound of representing with following formula that uses.
R 20 mSn(OCOR 21) 4-m
At this, R 20Be the alkyl of carbon number 1～8, be preferably the alkyl of carbon number 1～8, more preferably the alkyl of carbon number 4～8.R 21Be the replacement or the unsubstituted alkyl of carbon number 1～17, be preferably the replacement or the unsubstituted alkyl of carbon number 1～17.As substituting group, preferred carbon number is 1～4 alkyl.M is 0～3 integer.
Representative example as this curing catalysts; In organo-tin compound, can enumerate monobutyl three (2 ethyl hexanoic acid) tin, dimethyl two neodecanoic acid tin, two (2 ethyl hexanoic acid) tin of dibutyl, monobutyl three (normal-butyl propionic acid) tin, acid dibutyl tin, single hexyl three tin octoates, dihexyl two tin octoates, three hexyl list tin octoates, single hexyl three (citraconic acid) tin, dioctyl oxalic acid tin, the single tin acetate of trioctylphosphine, two (citraconic acid) tin of dioctyl, single octyl group three (methylpropanoic acid) tin, dioctyl dipropionic acid tin, the single propionic acid tin of trioctylphosphine, single octyl group three tin octoates, dioctyl two tin octoates, the single tin octoate of trioctylphosphine etc.These both can use separately, also can two or more mixing use.
As the representative example of organic titanic compound, can enumerate alkoxy titanium compounds such as tetra isopropyl titanate, four titanium butoxide acid esters, four octyl group titanate esters; The titanium chelate compound of titanium acetylacetone class, ethylacetoacetate titanium class etc. etc.These both can use separately, also can two or more mixing use.
As the representative example of organic zirconate, can enumerate the zirconium alkoxide compound of zirconium tetraisopropoxide, tetrabutyl zirconate, four octyloxy zirconiums etc.; The zirconium chelate compound of tetrem acyl acetone zirconium, four ethyl acetoacetate zirconiums, tripropoxy acetylacetone,2,4-pentanedione zirconium etc. etc.These both can use separately, also can two or more mixing use.
As the representative example of tertiary amine compound, can enumerate dimethylethanolamine, trivinyl diamines, methyl hydroxyethyl piperazine, dimethylamino ethoxy monoethanolamine etc.These both can use separately, also can two or more mixing use.
Representative example as quarternary ammonium salt compound; For example can enumerate 2-hydroxyethyl three normal-butyl ammoniums 2; 2-dimethyl propylene acid esters, 2-hydroxyethyl three normal-butyl ammoniums 2; 2-dimethyl butyrate acid esters, 2-hydroxypropyl three normal-butyl ammoniums 2,2-dimethyl propylene acid esters, 2-hydroxypropyl three normal-butyl ammoniums 2,2-dimethyl butyrate acid esters etc.These both can use separately, also can two or more mixing use.
With respect to (A) composition of 100 weight portions and (B) total amount of composition, (C) content of composition is 0.001～0.4 weight portion, is preferably 0.002～0.3 weight portion.When the content of (C) composition is lower than 0.001 weight portion, can't obtain promoting the effect of cross-linking reaction, when surpassing 0.4 weight portion, the connecting airtight property reduction of the ground floor and the second layer, thereby not preferred.
(triazines ultra-violet absorber (D))
(D) composition is the triazines ultra-violet absorber with following formula (D) expression.(D) composition can improve its dispersiveness through the cycloalkyl in the acrylic copolymer of (A) composition, can effectively hang down performance ultraviolet radiation absorption function.Its result, ground floor of the present invention has excellent weatherability.
Figure S2007800017034D00181
In the formula, R 4The expression carbon number is 1～18, be preferably 3～16, more preferably 4～8 alkyl, with-CH 2CH (OH) CH 2O-R 8The substituting group of expression or with-CH (CH 3) C (O) O-R 9The substituting group of expression.R 8The expression carbon number is 1～18, is preferably 3～16, more preferably 6～14 alkyl.R 9The expression carbon number is 1～18, is preferably 3～16, more preferably 6～10 alkyl.As R 4, R 8, R 9Alkyl, can enumerate ethyl, propyl group, butyl, amyl group, hexyl etc.
R 5Expression hydrogen atom, the alkyl of carbon number 1～18 or the alkoxyl of carbon number 1～18.The carbon number of alkyl is preferably 1～8, more preferably 1～4.
As alkyl, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl etc.The carbon number of alkoxyl is preferably 1～8, and more preferably 1～4.As alkoxyl, can enumerate methoxyl group, ethyoxyl, propoxyl group, butoxy etc.
R 6, R 7Represent independently respectively hydrogen atom, carbon number 1～18 alkyl, carbon number 1～18 alkoxyl or can be by the alkyl of carbon number 1～18 or the substituted phenyl of halogen atom.
The carbon number of alkyl is preferably 1～8, more preferably 1～4.As alkyl, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl etc.The carbon number of alkoxyl is preferably 1～8, more preferably 1～4.As alkoxyl, can enumerate ethyoxyl, propoxyl group, butoxy etc.The carbon number of the substituted alkyl on the phenyl is preferably 3～16, and more preferably 4～8.As alkyl, can enumerate ethyl, propyl group, butyl, amyl group, hexyl etc.As halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms etc.
V representes the alkyl of hydrogen atom, OH base or carbon number 1～12.The carbon number of alkyl is preferably 1～8, more preferably 1～4.As alkyl, can enumerate ethyl, propyl group, butyl, amyl group, hexyl etc.
As triazines ultra-violet absorber with formula (D) expression, can enumerate the following ultra-violet absorber that CibaSpecialty Chemicals Inc. makes particularly, that is,
(1) チ ヌ PVC Application 1557 (R 4Be hexyl, R 5, R 6, R 7And V is a hydrogen atom);
(2) チ ヌ PVC Application 400 (R 4For-CH 2CH (OH) CH 2O-R 8(R 8Be dodecyl and tridecyl), R 5, R 6, R 7And V is a hydrogen atom);
(3) チ ヌ PVC Application 405 (R 4For-CH 2CH (OH) CH 2O-R 8(R 8Be octyl group), R 5, R 6, R 7And V is a methyl);
(4) チ ヌ PVC Application 460 (R 4Be butyl, R 5, R 6, R 7Be butoxy, V is the OH yl);
(5) チ ヌ PVC Application 479 (R 4For-CH (CH 3) C (O) O-R 9(R 9Be octyl group), R 5Be hydrogen atom, R 6And R 7Be phenyl, V is a hydrogen atom).
These both can use separately, also can two or more mixing use.The preferred mixing used the different ultra-violet absorber of two or more very big absorbing wavelength; Thereby can absorb ultraviolet ray in the wideer wavelength region may of ultraviolet region; And, with the ultraviolet ray of the wavelength region may a little less than the absorption of side's ultra-violet absorber, absorb by the opposing party's ultra-violet absorber; Can improve the durability with respect to UV of ultra-violet absorber self thus, thus preferred.
With respect to (A) composition of 100 weight portions and (B) total amount of composition, content that should (D) composition is 0～40 weight portion, is preferably 0～30 weight portion.When surpassing 40 weight portions, the connecting airtight property reduction between ground floor and base material or ground floor and the second layer.
(other compositions)
In the acrylic acid resin composition, can also contain the hydrolytic condensate of silane coupling agent and/or silane coupling agent.Through containing the hydrolytic condensate of silane coupling agent and/or silane coupling agent, can improve the connecting airtight property between base material and ground floor, ground floor and the second layer, can keep this connecting airtight property in long-term the use.
As this silane coupling agent, can enumerate 3-TSL 8330,3-aminopropyltriethoxywerene werene, γ-(2-amino-ethyl) TSL 8330, γ-(2-amino-ethyl) aminopropyltriethoxywerene werene, γ-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, γ-(2-amino-ethyl) aminopropyl methyldiethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxysilane, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane hydrochloride, N-β-(N-vinyl benzyl amino-ethyl)-γ-An Jibingjisanyiyangjiguiwan hydrochloride, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, vinyl triacetyl silane, γ-phenylamino propyl trimethoxy silicane, γ-phenylamino propyl-triethoxysilicane, vinyltrimethoxy silane, VTES, octadecyl dimethyl [3-(trimethoxysilyl) propyl group] ammonium chloride, octadecyl dimethyl [3-(triethoxysilyl) propyl group] ammonium chloride, γ-urea groups propyl trimethoxy silicane, γ-urea groups propyl-triethoxysilicane, 3-isocyanates propyl trimethoxy silicane, 3-isocyanates propyl-triethoxysilicane etc.
The hydrolytic condensate of silane coupling agent and/or silane coupling agent both can have been used separately also and can two or more mixing use.With respect to (A) composition of 100 weight portions and (B) total amount of composition, the content of the hydrolytic condensate of this silane coupling agent and/or silane coupling agent is preferably 0.1～10 weight portion, more preferably 0.2～8 weight portion.
In acrylic acid resin composition, further can also use the ultra-violet absorber beyond (D) composition.As this ultra-violet absorber, for example can enumerate 2,4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-octyloxy benzophenone, 2,2 '-dihydroxy-4, the benzophenone of 4 '-dimethoxy-benzophenone etc.; The benzotriazole of 2-(5 '-methyl-2 '-hydroxy phenyl) BTA, 2-(3 '-tert-butyl group-5 '-methyl-2 '-hydroxy phenyl) BTA, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-5-chlorobenzotriazole etc.; Ethyl-2-cyanic acid-3,3-diphenylacrylate ester, 2-ethylhexyl-2-cyanic acid-3, the cyanoacrylate of 3-diphenylacrylate ester etc.; The salicylate class of phenyl salicylic acid esters, OPS p octylphenyl salicylate etc.; Diethyl-to the toluenyl malonic ester class of methoxyl group toluenyl malonic ester, two (2-ethylhexyl) toluenyl malonic ester etc.; 2-(2 '-hydroxy-5-methyl base acryloxy ethylphenyl)-2H-BTA with can with the copolymer of the vinyl monomer of this monomer copolymerizable, 2-(2 '-hydroxyl-5-acryloxy ethylphenyl)-2H-BTA with can with the metal oxide microparticle subclass of the copolymer of the vinyl monomer of this monomer copolymerizable, titanium oxide, cerium oxide, zinc oxide, tin oxide, tungsten oxide, zinc sulphide, cadmium sulfide etc.With respect to (A) composition of 100 weight portions and (B) total amount of composition, the content of this ultra-violet absorber is preferably 0.1～30 weight portion, more preferably 0.5～20 weight portion.
Among the present invention, on acrylic acid resin composition, can also add light stabilizer.As light stabilizer, for example can enumerate methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidyl ester, two capric acid two (2,2; 6,6-tetramethyl-1-octyloxy-4-piperidyl) ester, malonic acid two (1,2,2,6,6-pentamethyl-4-piperidyl)-{ [3,5-two (1; The 1-dimethyl ethyl)-and the 4-hydroxy phenyl] methyl } butyl ester, 2, two [N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-2-yl) amino]-6-(the 2 hydroxy ethylamine)-1,3,5-triazines of 4-, decanedioic acid two (1; 2,2,6,6-pentamethyl-4-piperidyl) ester, decanedioic acid methyl (1,2,2,6; 6-pentamethyl-4-piperidines) ester, two (2,2,6,6-tetramethyl-4-piperidyl) carbonic ester, two (2,2,6, the 6-tetramethyl-4-piperidyl) esters of succinic acid, decanedioic acid two (2; 2,6,6-tetramethyl-4-piperidyl) ester, 4-benzoyloxy-2,2,6,6-tetramethyl piperidine, the hot acyloxy-2,2 of 4-; 6,6-tetramethyl piperidine, two (2,2,6,6-tetramethyl-4-piperidyl) diphenyl methane-p, p '-diurethane, two (2,2; 6,6-tetramethyl-4-piperidyl) benzene-1, hindered amines such as 3-disulfonate, two (2,2,6,6-tetramethyl-4-piperidyl) phenyl-phosphonite ester; Two octyl phenyl nickel sulfides, 3, the nickel complex of 5-di-tert-butyl-4-hydroxyl benzyl mono phosphoric acid ester ethanol nickel salt complex compound, nickel dibutyl dithiocarbamate etc.These light stabilizers both can use separately, also can two or more combinations use.With respect to (A) composition of 100 weight portions and (B) total amount of composition, the content of this light stabilizer is preferably 0.01～50 weight portion, more preferably 0.05～10 weight portion.
(solvent)
Ground floor can form through acrylic acid resin composition (coating) is coated on substrate surface.The preferred acrylic resins composition also contains solvent.
Preferred solvent is not for reacting and do not dissolve the solvent of base material with base material.As this solvent, can enumerate the ketone of acetone, MEK, methyl isopropyl Ketone, cyclohexanone etc.; Oxolane, 1,4-diox, 1, the ethers of 2-dimethoxy-ethane etc.; The ester class of ethyl acetate, acetic acid ethoxy ethyl ester etc.; The alcohols of methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, 2-methyl-2-propyl alcohol etc.; The hydro carbons of n-hexane, normal heptane, isooctane, benzene,toluene,xylene, gasoline, light oil, kerosene etc.; Acetonitrile, nitromethane, water etc.These both can use separately, also can two or more mixing use.
The concentration of the resin in the acrylic acid resin composition (solid constituent) is preferably 1～50 weight %, 3～30 weight % more preferably.
< organosiloxane resins composition >
The organosiloxane resins composition contains the hydrolytic condensate (F composition) of cataloid (E composition), alkoxy silane and the metal oxide (G composition) that contains as required.
(cataloid (E))
As cataloid (E composition), be that preferred diameter is the silicon dioxide particles of 5～200nm, more preferably diameter is the silicon dioxide particles of 5～40nm is dispersed into colloidal in water or organic solvent a cataloid.
As this cataloid, can enumerate following material particularly, that is,, can enumerate the ス ノ one テ Star Network ス O of daily output chemical industry (strain), the カ タ ロ イ De SN30 that catalyst changes into industry (strain) as the commodity that are dispersed in the acidic aqueous solution; As the commodity that are dispersed in the alkaline aqueous solution, can enumerate ス ノ one テ Star Network ス 30, the ス ノ one テ Star Network ス 40 of daily output chemical industry (strain), catalyst changes into カ タ ロ イ De S30, the カ タ ロ イ De S40 of industry (strain); As the commodity that are dispersed in the organic solvent, can enumerate the MA-ST, IPA-ST, NBA-ST, EG-ST, XBA-ST, NPC-ST, DMAC-ST of daily output chemical industry (strain) etc.
Cataloid can use any one in water-dispersion type and the organic solvent decentralized, but preferably adopts water-dispersion type.When adopting the cataloid of water-dispersion type, there is a large amount of hydroxyls in the surface of silicon dioxide particles, and this hydroxyl combines with the hydrolytic condensate of alkoxy silane securely, therefore, thinks to obtain the excellent more plastic lamination body of mar proof.In addition; This water-dispersion type cataloid can use any one in acidic aqueous solution decentralized and the alkaline aqueous solution decentralized; But consider the diversity of curing catalysts selection, the appropriate hydrolysis of trialkoxy silane, the realization of condensed state etc., preferably adopt acidic aqueous solution decentralized cataloid.
(hydrolytic condensate of alkoxy silane (F))
The hydrolytic condensate of alkoxy silane (F composition) is that the alkoxy silane with following formula (F) expression is hydrolyzed condensation reaction and obtains.
R 1 mR 2 nSi(OR 3) 4-m-n (F)
In the formula, R 1, R 2Represent independently that respectively carbon number is 1～4 alkyl, vinyl or selected free methyl acryloxy, amino, glycidoxy and 3, a substituted carbon number of above group in the group that the 4-epoxycyclohexyl is formed is 1～3 alkyl.Preferred R 1, R 2Represent the alkyl of carbon number 1～4 respectively independently, be preferably methyl especially.
R 3Alkyl or vinyl for carbon number 1～4.Preferred R 3Be the alkyl of carbon number 1～3, be preferably methyl or ethyl especially.M, n represent the arbitrary integer in 0,1,2 respectively independently, and m+n is the arbitrary integer in 0,1,2.Preferred m, n are respectively 0 or 1.In addition, preferred m+n is 1.
As alkoxy silane; Can enumerate tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisobutoxy-silicane alkane, MTMS, MTES, ethyl trimethoxy silane, isobutyl group trimethoxy silane, vinyltrimethoxy silane, VTES, γ-methacryloxypropyl trimethoxy silane, β-(3 particularly; The 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, N-β (amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl)-γ-An Jibingjisanyiyangjiguiwan, dimethyldimethoxysil,ne, dimethyldiethoxysilane, vinyl methyl dimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 3-aminopropyl methyldiethoxysilane etc.; Wherein, The preferred alkyl trialkoxy silane, special preferable methyl trimethoxy silane and MTES.These both can use separately, also can mix use.Further, flexible in order to give to cured film according to purposes, also preferably two degree of functionality alkoxy silanes of dimethyldimethoxysil,ne etc. are mixed and use.
In addition, particularly as the organosiloxane resins composition that is used to form the second layer of excellent in wear resistance, 70～100 weight % in the preferred alkoxy silane are methyl trialkoxysilane.
(F) composition is the mixture of the part of a part of of alkoxy silane or the material that all is hydrolyzed and this hydrolysate or the condensation product that all carries out condensation reaction etc., and these can obtain through making it carry out solgel reaction.
(E) composition in the organosiloxane resins composition and (F) content of composition depend on the transparency, mar proof, marresistance, the connecting airtight property of the stability of organosiloxane resins composition, resulting cured film and have or not the aspect such as to crack.When with the total amount of (E) composition and (F) composition during as 100 weight %, the preferred mixed proportion of these two compositions is that (E) composition is 10～60 weight %, is converted into R 1 mR 2 nSiO (4-m-n)/2(F) composition be 40～90 weight %, more preferably (E) composition is 10～40 weight %, is converted into R 1 mR 2 nSiO (4-m-n)/2(F) composition be 60～90 weight %.
Contain (E) composition and (F) the organosiloxane resins composition of composition, can prepare through the hydrolysis-condensation reaction that carries out alkoxy silane.
The water that the hydrolysis of alkoxy silane is required when using the cataloid dispersion liquid of water-dispersion type, is supplied with by this dispersion liquid, if desired, can also further add water.With respect to the alkoxy silane of 1 equivalent, use the water of 1～10 equivalent usually, preferably use the water of 1.5～7 equivalents.
The hydrolysis-condensation reaction of alkoxy silane must carry out under acid condition, in order under this condition, to be hydrolyzed, adopts acid as hydrolytic reagent usually.As this acid, can be added in advance in alkoxy silane or the cataloid dispersion liquid, add after can also both being mixed.In addition, this interpolation can once or at twice be accomplished.As this acid, can enumerate the inorganic acid of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid etc.; The organic acid of formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, butanedioic acid, maleic acid, lactic acid, p-methyl benzenesulfonic acid etc.; The viewpoint of calm pH value easy to control is set out; The organic carboxyl acid of preferred formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, butanedioic acid, maleic acid etc., preferred especially acetic acid.When using inorganic acid,, more preferably use with 0.001～0.1 equivalent concentration preferably with 0.0001～2 equivalent concentration.When using organic acid, with respect to the alkoxy silane of 100 weight portions, preferably at 0.1～50 weight portion, more preferably use in the scope of 1～30 weight portion.
The condition of hydrolysis-condensation reaction is along with the kind of the cataloid that coexists in the kind of employed alkoxy silane, the system and their amount and change; Therefore cannot treat different things as the same, but the reaction temperature of system is that 20～70 ℃, reaction time are 1 hour～several days usually.When adopting said method, can not produce deposition, can obtain the more excellent second layer of mar proof.
(metal oxide (G))
Preferably have the organic siloxane resin combination and contain metal oxide (G).Can improve weatherability through (G) composition.As (G) composition, be selected from least a metal oxide in the group of forming by titanium oxide, zinc oxide, cerium oxide, tin oxide, tungsten oxide, because its light decomposition is little, thereby preferred the use.Especially preferably use titanium oxide.With respect to the total amount of the E composition and the F composition of 100 weight portions, (G) content of composition is preferably 0.1～15 weight portion, 0.2～5.0 weight portion more preferably.
(curing catalysts (I))
Preferably have the organic siloxane resin combination and also contain curing catalysts as (I) composition.As this curing catalysts, can enumerate the alkali metal salt of the lithium salts, sodium salt, sylvite etc. of aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, tartaric acid, butanedioic acid; And the quaternary ammonium salt of benzyl trimethyl ammonium salt, choline salt, tetramethyl ammonium, tetraethyl ammonium salt etc., particularly, can preferably use sodium acetate, potassium acetate, choline acetate, acetic acid benzyltrimethylammon.um.With respect to (E) composition of 100 weight portions and (F) total amount of composition, the content of preferred consolidation catalyst (I) is 0.01～10 weight portion, 0.1～5 weight portion more preferably.
(solvent)
The second layer can form through organosiloxane resins composition (coating) is coated on the ground floor.Preferably have the organic siloxane resin combination and contain solvent.
As solvent, the organosiloxane resins composition must stably be dissolved in wherein, for this reason, hopes to adopt more than at least 20 weight %, is the solvent of alcohol more than the preferred 50 weight %.
As this alcohol, can enumerate methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, 2-methyl isophthalic acid-propyl alcohol, cellosolvo, 4-methyl-2-amylalcohol, butoxy ethanol etc. particularly.Wherein, the low-boiling point alcohol of preferred carbon number 1～4, when considering dissolubility, stability and coating, preferred especially 1-butanols, 2-propyl alcohol.
Also contain acid in the solvent, this acid be for the moisture of not participating in hydrolysis in the water of regulating the water-dispersion type cataloid, be accompanied by the hydrolysis of alkoxy silane and the lower alcohol that produces, with an organic solvent the organic solvent of its decentralized medium during the cataloid of decentralized, be coated with the pH value of application organosiloxane resins composition and add.
As being used for the acid that pH regulates, can enumerate the inorganic acid of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid etc.; The organic acid of formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, butanedioic acid, maleic acid, lactic acid, p-methyl benzenesulfonic acid etc.; The viewpoint of calm pH value easy to control is set out, the organic carboxyl acid of preferred formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, butanedioic acid, maleic acid etc.
As other operable solvents, must mix with water/alcohol, for example can enumerate the ketone of acetone, MEK, methyl iso-butyl ketone (MIBK) etc.; Oxolane, 1,4-diox, 1, the ethers of 2-dimethoxy-ethane etc.; Ester classes such as ethyl acetate, n-butyl acetate, isobutyl acetate, acetic acid ethoxy ethyl ester.
With respect to (E) composition of 100 weight portions and (F) total amount of composition, the content of preferred solvent is 50～2000 weight portions, 150～1400 weight portions more preferably.The concentration of solid constituent is preferably 5～70 weight %, 7～40 weight % more preferably.
Preferably through regulating the content of acid and curing catalysts, the pH value of organosiloxane resins composition preferably is adjusted at 3.0～6.0 scope, more preferably is adjusted at 4.0～5.5 scope.When pH value during in this scope, can prevent the gelation of the organosiloxane resins composition under the normal temperature, increase storage stability.The organosiloxane resins composition further carries out several hours to several days slaking to it usually, thereby becomes stable coating.
In the organosiloxane resins composition, its (E), (F) and (G) composition dissolving and/or be dispersed in the solvent, and preferred (i) is converted into R when the weight with (F) composition 1 mR 2 nSiO (4-m-n)/2During weight, with respect to (E) composition of 100 weight % and (F) summation of composition, (E) composition is that 10～60 weight %, (F) composition are 40～90 weight %, and with respect to (E) composition of 100 weight portions and (F) summation of composition, (G) composition is 0.1～15 weight portion; (ii) in the laser diffractometry particle size distribution of (G) composition, in the time of will accumulating 50% particle diameter and accumulate 90% particle diameter respectively as D50 and D90, D90 is below the 100nm, and D90/D50 is below 20.
Preferable alloy oxide (G) is titanium oxide, zinc oxide or cerium oxide.To have filled average grain diameter be the medium grinding machine of the medium below the 100 μ m to preferable alloy oxide (G) in order to use, and the slurries that metal oxide are dispersed in water or organic solvent are carried out dispersion treatment and the metal oxide that obtains.Preferably (E), (F) and (G) concentration of the total amount of composition be 5～70 weight %.Preferred solvent contains the alcohol of the above carbon number 1～4 of 50 weight %.Further, with respect to (E) of 100 weight portions and (F) total amount of composition, the content of preferred consolidation catalyst (I) is 0.01～10 weight portion.
< duplexer >
(ground floor)
In the present invention; Ground floor can be through being coated on substrate surface with acrylic acid resin composition (coating); Then remove solvent with methods such as heating, further heat, crosslinked (heat cure) forms so that hydroxyl and the NCO that generates because of heating react also.
When being coated on coating on the base material, can be according to the substrates coated shape, suitably select rod to be coated with method, dip coating, cast and be coated with methods such as method, spraying process, spin-coating method, rolling method.Be coated with the base material of acrylic acid resin composition, under the temperature below the heat distortion temperature of normal temperature to base material, carry out drying, the removal of solvent usually, make it heat cure.
When heat cure is carried out under the high temperature of the scope that can not impact the hear resistance of base material, can accomplish curing as early as possible, thereby preferred.In addition, at normal temperatures, heat cure can not carried out fully, can not become the coating with the desired sufficient crosslink density of ground floor.In this curing process, the crosslinkable groups in the thermohardening type acrylic acid resin composition is reacted, thereby the crosslink density of coating rises, and becomes the coating of the excellent in te pins of durability under connecting airtight property, hot water resistance, the hot environment.
Heat curing temperature is preferably 80～160 ℃, more preferably 100～140 ℃, further is preferably 110～130 ℃.Thermal curing time is preferably 10 minutes～and 3 hours, more preferably 20 minutes～2 hours.It is crosslinked through heating crosslinkable groups to be carried out, and obtains range upon range of as the duplexer of the acrylate resin layer of ground floor.When thermal curing time is less than 10 minutes, can not fully carry out cross-linking reaction, obtain the durability under the hot environment, the ground floor of weatherability shortcoming sometimes.In addition, see that thermal curing time can fully achieve the goal with interior at 3 hours from the performance of acrylic acid resin composition.
Form ground floor through acrylic acid resin composition is carried out heat cure, can access and the connecting airtight property advantages of good abrasion property of the second layer and base material and the duplexer that has excellent weather resistance.
The thickness of ground floor is preferably 1～20 μ m, more preferably 2～10 μ m.When thickness during less than 1 μ m, ultraviolet transmitance is high, produces the phenomenon of base material flavescence, the reduction of connecting airtight property, so weatherability shortcoming.When thickness surpassed 20 μ m, because internal stress increases, and cross-linking reaction was carried out insufficiently during heat cure, therefore, becomes the layer of the durability of shortcoming under hot environment.In addition, the volatilization of the solvent during the acrylic resins of painting composition is insufficient, and solvent remains in the ground floor, damages hot water resistance, weatherability thus.
(second layer)
The second layer can be through being coated on organosiloxane resins composition (coating) on the ground floor, carries out heat cure then and form.The formation of the preferred second layer is the formation of then ground floor and carrying out continuously.
As coating process, can be according to the substrates coated shape, suitably select rod to be coated with method, dip coating, cast and be coated with methods such as method, spraying process, spin-coating method, rolling method.After being coated with the organosiloxane resins composition, usually under the temperature below the heat distortion temperature of normal temperature to base material, carry out solvent drying, remove after, make it heat cure.When heat cure is carried out under the high temperature of the scope that can not impact the hear resistance of base material, can accomplish curing as early as possible, thereby preferred.In addition, at normal temperatures, heat cure can not carried out, and can not obtain solidifying tunicle.This means that part has produced condensation in the organosiloxane in the coating.In this curing process, residual Si-OH causes condensation reaction and forms the Si-O-Si key, becomes the coating of excellent in wear resistance.
Heat curing temperature is preferably 50～200 ℃, more preferably 80～160 ℃, further is preferably 100～140 ℃.Thermal curing time is preferably 10 minutes～and 4 hours, more preferably 20 minutes～3 hours, further be preferably 30 minutes～2 hours.
Second layer thickness is preferably 1～20 μ m, and more preferably 2～10 μ m further are preferably 3～8 μ m.When the thickness of the second layer during, the phenomenons such as connecting airtight property reduction of stress between second layer generation crackle or the second layer and ground floor that produces in the time of can not occurring because of heat cure, can obtain the second layer with sufficient mar proof of the object of the invention in this scope.
(levelling agent)
In the present invention, in order to improve the flatness of coating and resultant layer, can ground floor and the second layer with coating in the known levelling agent of interpolation.
As this levelling agent, can enumerate Dow Corning Toray Silicone Co., silicon compound SH200-100cs, SH28PA, SH29PA, SH30PA, ST83PA, ST80PA, ST97PA, ST86PA, SH21PA that Ltd makes; Silicon compound KP321, KP322, KP323, KP324, KP326, KP340, KP341 that SHIN-ETSU HANTOTAI's chemical industry (strain) is made; The fluorine class surfactant F-179 that big Japanese ink chemical industry (strain) is made, F-812A, F-815 etc.These levelling agents both can use separately, also can two or more and usefulness.With respect to the resin of 100 weight portions, the use amount of this levelling agent is preferably 0.0001～2.0 weight portion, more preferably 0.0005～1.0 weight portion.
In the scope of not damaging the object of the invention, in ground floor and second layer coating, can also add dyestuff, pigment, filler etc.In addition, flexible in order to improve, also can add acrylic resin.
(base material)
As being used for base material of the present invention, can enumerate the acrylic resin of polycarbonate resin, polymethyl methacrylate etc. particularly; PETG, polybutylene terephthalate (PBT), gather 2, the mylar of 6-(ethylene naphthalate) etc.; Polystyrene, polypropylene, polyacrylate, polyether sulfone etc.These resins both can use separately, also can two or more mixing use.
As the base material that has with the adherence of ground floor and excellent mar proof, optimization polycarbonate resin, acrylic resin, special optimization polycarbonate resin.
As an example of polycarbonate resin, can enumerate binary phenol and carbonic ester presoma are reacted the polycarbonate resin that obtains through interface polycondensation or fusion method etc.As the representative example of binary phenol, can enumerate 2, two (4-hydroxy phenyl) propane (being referred to as bisphenol-A usually), 2 of 2-, two (3-methyl-4-hydroxy phenyl) propane, 2 of 2-; Two (3, the 5-dimethyl-4-hydroxy phenyl) propane, 1 of 2-, two (4-hydroxy phenyl) ethane, 1 of 1-, 1-bis(4-hydroxyphenyl)cyclohexane, 2; Two (4-hydroxy phenyl) butane, 2 of 2-, two (4-the hydroxy phenyl)-3-methybutanes, 9 of 2-, two [(4-hydroxy-3-methyl) phenyl] fluorenes, 2 of 9-; Two (the 4-hydroxy phenyls)-3 of 2-, 3-dimethylbutane, 2, two (4-the hydroxy phenyl)-4-methylpentanes, 1 of 2-; Two (the 4-hydroxy phenyls)-3,3 of 1-, 5-trimethyl-cyclohexane, α; Diisopropyl benzene, two (4-hydroxy phenyl) sulfide, two (4-hydroxy phenyl) sulfone etc. between α '-two (4-hydroxy phenyl), wherein, preferred bisphenol-A.These binary phenol both can use separately, also can two or more mixing use.
As the Merlon precursor, use carboxylic acid halides (Carbonyl halide), carbonic ester or haloformate (Ha ロ ホ Le メ one ト) etc., specifically, can enumerate the bishaloformate of phosgene (Phosgene), diphenyl carbonate or binary phenol etc.
When through interface polycondensation or fusion method, when making polycarbonate resin, also can use catalyst, end to stop agent, anti-oxidant etc. as required by binary phenol and carbonic ester precursor, wherein anti-oxidant is in order to prevent the oxidation of binary phenol.In addition; Polycarbonate resin both can be with the branched polycarbonate resin of combined polymerization in addition of the multifunctional aromatic compound more than the three-functionality-degree; Also can be with aromatic series or the aliphatic two degree of functionality carboxylic acids polyestercarbonate resin of combined polymerization in addition; In addition, also can be with the two or more mixtures that mix of resulting polycarbonate resin.
The molecular weight of polycarbonate resin is preferably 10000～50000 when representing with viscosity average molecular weigh (M), and more preferably 15000～35000.Polycarbonate resin with this viscosity average molecular weigh has full intensity, and the melt fluidity during moulding is also good.The said viscosity average molecular weigh of the present invention can be calculated according to following method.At first, from the solution that under 20 ℃, the 0.7g polycarbonate resin is dissolved in the 100ml carrene and obtains, obtain specific viscosity (η Sp), and substitution following formula and calculating:
η Sp/ c=[η]+0.45 * [η] 2C ([η] is limiting viscosity)
[η]＝1.23×10 -4M 0.83
c＝0.7。
In this polycarbonate resin, can add the stabilizing agent of phosphite ester, phosphate, phosphonate ester etc. as required; The fire retardant of the low-molecular polycarbonate of tetrabromobisphenol A, tetrabromobisphenol A, ten bromophenols etc.; Colouring agent; Lubricant; Other resins of above-mentioned mylar or ABS etc. etc.
Duplexer of the present invention has high-caliber weatherability, has mar proof, hot water resistance, to the durability of environmental change and the sufficient durability under the hot environment.
Duplexer, it is formed at the ground floor and the second layer at least one side surface of base material, and preferred ground floor satisfies following formula (1)～(4) and the second layer satisfies following formula (5)～(8).
0.1≤P(Abs 0)≤2 (1)
1≤P(d)≤20 (2)
1≤P(Abs 0)×P(d)≤40 (3)
{P(Abs)/P(Abs 0)}×100≥90 (4)
Wherein, P (Abs 0) be the absorbance of ground floor under wavelength 300nm of per 1 μ m; P (Abs) is for carrying out this duplexer the absorbance of ground floor under wavelength 300nm of the per 1 μ m after 500 hours the exposure test in climatic cabinet (Super Xenon Weather), P (d) is ground floor thickness (μ m).
0.01≤T(Abs 0)≤2 (5)
1≤T(d)≤20 (6)
0.1≤T(Abs 0)×T(d)≤40 (7)
{T(Abs)/T(Abs 0)}×100≥90 (8)
Wherein, T (Abs 0) be the absorbance of the second layer under wavelength 300nm of per 1 μ m; T (Abs) is for carrying out this duplexer the absorbance of the second layer under wavelength 300nm of the per 1 μ m after 500 hours the exposure test in climatic cabinet (Super Xenon Weather), T (d) is second layer thickness (μ m).
On being formed at base material each can obtain light absorpting ability and light absorpting ability conservation rate duplexer excellent, that have high-caliber weatherability layer in the scope of formula (1)～(8) time.In addition, when in the scope of formula (1)～(8), the connecting airtight property excellence of base material and ground floor, ground floor and the second layer, the generation of crackle also reduces.
In addition, preferred substrates is a transparent plastic, and the difference of the haze value of the plastic lamination body behind the haze value of the living plastic basis material before range upon range of ground floor and the second layer and the range upon range of ground floor and the second layer is below 1%, more preferably below 0.5%.
Duplexer of the present invention can be formed at the protective layer that is made up of the ground floor and the second layer two sides of base material.The all protected duplexer in this two sides is suitable in automobile glass pane or the movable roof.
The invention effect
In the duplexer of the present invention,, therefore, can in the ultraviolet radiation absorption effect of performance excellence, bring into play its effect in Sustainable Stability ground because the triazines ultra-violet absorber is included in the ground floor with the acrylic resin copolymer that contains cycloalkyl.Therefore, duplexer of the present invention has excellent weatherability.If the second layer contains ultra-violet absorber, can further improve its weatherability.Because duplexer of the present invention contains urethane bonds in ground floor, therefore, its with the base material and the second layer between connecting airtight property and hot water resistance excellence.In addition, duplexer of the present invention has excellent outward appearance, the transparency and mar proof.
Through adopting acrylic acid resin composition of the present invention, can in this duplexer, form the excellent ground floor of weatherability and connecting airtight property.
Through adopting organosiloxane resins composition of the present invention, can in this duplexer, form the excellent second layer of weatherability, mar proof and connecting airtight property.
Utilizability on the industry
Duplexer of the present invention; Can be suitable for glass pane, the movable roof of aircraft, vehicle, automobile etc.; The glass pane of building machinery; The glass pane in restaurant, dwelling house, greenhouse etc., the roof of garage, arcuated construction is in the lens of headlamp lens, optical lens, speculum, glasses, goggles, sound-proof wall, signal lamp, elbow reflection mirror, bicycle windscreen, label, automobile pillar, automobile exterior panel, other various plates, the film etc.
Embodiment
Below, through embodiment further explain the present invention, but the present invention is not limited to these embodiment.In addition, part and the % among the embodiment representes weight portion and weight %.
[I]
(synthesizing of acrylic acid copolymer soln (A)～(H))
[reference example I-1]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, adding 79.9 parts EMA (being designated hereinafter simply as " EMA "), 33.6 parts cyclohexyl methacrylate (being designated hereinafter simply as " CHMA "), methacrylic acid-2-hydroxy methacrylate (being designated hereinafter simply as " HEMA ") of 13.0 parts, 126.6 parts methyl iso-butyl ketone (MIBK) (being designated hereinafter simply as " MIBK ") and 63.3 parts 2-butanols (being designated hereinafter simply as " 2-BuOH ") and also mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.33 part azodiisobutyronitrile (being designated hereinafter simply as " AIBN "), in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.6% acrylic acid copolymer soln (A).By GPC measure (post: Shodex GPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 125000.
[reference example I-2]
Have reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, adding 74.2 parts of EMA, 33.6 parts CHMA, 13.0 parts HEMA, 12.0 parts the LA-82 (methacrylate that contains hindered amines photostability group; Methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidines ester, R in formula (A-5) 10Be the compound of methyl, rising sun electrochemical industry (strain) is made), the 2-BuOH of 132.8 parts MIBK and 66.4 parts and mixing.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.33 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.7% acrylic acid copolymer soln (B).By GPC measure (post: Shodex GPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 115000.
[reference example I-3]
With a reflux condenser and a stirrer and purged with nitrogen in a flask, add 75.9 parts of EMA, 33.6 parts of CHMA, 13.0 parts HEMA, 2.4 parts of LA-82, 8.1 parts of RUVA-93 (containing an ultraviolet absorbing groups methacrylate; 2 - (2'-hydroxy-5'-methacryloyloxy-ethyl-phenyl)-2H-benzotriazole, a large Peng Chemical (Co., Ltd.)), 133.0 parts of MIBK and 66.5 parts of 2-BuOH and mixed.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.33 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.5% acrylic acid copolymer soln (C).By GPC measure (post: Shodex GPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 120000.
[reference example I-4]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, adding 68.5 parts of EMA, 10.0 parts methyl methacrylate (MMA), 33.6 parts CHMA, 13.0 parts HEMA, 125.2 parts MIBK and 62.6 parts 2-BuOH and also mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.33 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.5% acrylic acid copolymer soln (D).By GPC measure (post: Shodex GPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 110000.
[reference example I-5]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, adding 102.7 parts EMA, 13.0 parts HEMA, 115.7 parts MIBK and 57.9 parts 2-BuOH and also mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.33 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.6% acrylic acid copolymer soln (E).By GPC measure (post: ShodexGPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 115000.
[reference example I-6]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, adding 51.4 parts EMA, 75.7 parts CHMA, 13.0 parts HEMA, 140.1 parts MIBK and 70.0 parts 2-BuOH and also mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.33 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.7% acrylic acid copolymer soln (F).By GPC measure (post: Shodex GPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 115000.
[reference example I-7]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, adding 57.1 parts EMA, 33.6 parts CHMA, 39.0 parts HEMA, 129.8 parts MIBK and 64.9 parts 2-BuOH and also mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.33 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.5% acrylic acid copolymer soln (G).By GPC measure (post: Shodex GPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 100000.
[reference example I-8]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, adding 79.9 parts EMA, 33.6 parts CHMA, 24.8 parts methacrylic acid trimethoxy-silylpropyl ester (TMSPMA), 138.4 parts MIBK and 69.2 parts 2-BuOH and also mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.33 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.5% acrylic acid copolymer soln (H).By GPC measure (post: Shodex GPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 105000.
Figure S2007800017034D00351
In addition, in table 1, each symbolic representation is following.
EMA: EMA
MMA: methyl methacrylate
CHMA: cyclohexyl methacrylate
HEMA: methacrylic acid-2-hydroxy methacrylate
LA-82: methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidines ester is as the R of the raw material of the repetitive of following formula (A-5) 10Be the monomer of methyl (ア デ カ ス タ Block LA-82 contains the methacrylate of hindered amines photostability group, and rising sun electrochemical industry (strain) is made)
TMSPMA: methacrylic acid trimethoxy-silylpropyl ester
RUVA: 2 - (2'-hydroxy-5'-methacryloyloxy-ethyl-phenyl)-2H-benzotriazole (RUVA-93, large Peng Chemical (Co., Ltd.))
MIBK: methyl iso-butyl ketone (MIBK)
The 2-BuOH:2-butanols
AIBN: azodiisobutyronitrile
(preparation of acrylic resin paint (i-1)～(i-17))
[reference example I-9]
In 100 parts aforesaid propylene acid copolymer solution (A), add 43.2 parts MIBK, 21.6 parts 2-BuOH, 83.5 parts 1-methoxyl group-2-propyl alcohol and mix, add 5.3 parts チ ヌ PVC Application 400 (triazines ultra-violet absorbers; Ciba Specialty Chemicals Inc. makes); And add 10.6 parts VESTANAT B1358/100 (Ltd. makes for polyisocyanate compounds presoma, DegussaJapan Co.); So that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (A) of 1 equivalent; NCO reaches 1.0 equivalents, further, adds 0.015 part dimethyl two neodecanoic acid tin (DMDNT); And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-1).
[reference example I-10]
In 100 parts aforesaid propylene acid copolymer solution (B); Add 42.9 parts MIBK, 21.4 parts 2-BuOH, 83.1 parts 1-methoxyl group-2-propyl alcohol and mix, add 5.3 parts チ ヌ PVC Application 400, and add 10.1 parts VESTANAT B1358/100; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (B) of 1 equivalent; NCO reaches 1.0 equivalents, further, adds 0.015 part dimethyl two neodecanoic acid tin; And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-2).
[reference example I-11]
In 100 parts aforesaid propylene acid copolymer solution (B), add 39.1 parts MIBK, 19.5 parts 2-BuOH, 79.3 parts 1-methoxyl group-2-propyl alcohol and mix, add 5.3 parts チ ヌ PVC Application 400; And add 10.1 parts VESTANAT B1358/100; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (B) of 1 equivalent, NCO reaches 1.0 equivalents, further; Add 0.015 part dimethyl two neodecanoic acid tin, 9.46 parts the APZ-6633 (solution of silane coupling agent hydrolytic condensate; Solid constituent is 5 weight %, and Nippon Unicar CompanyLimited makes), 2.75 parts LA-82 (hindered amine light stabilizer, rising sun electrochemical industry (strain) is made); And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-3).
[reference example I-12]
In 100 parts aforesaid propylene acid copolymer solution (B), add 39.1 parts MIBK, 19.5 parts 2-BuOH, 79.3 parts 1-methoxyl group-2-propyl alcohol and mix, add 5.3 parts チ ヌ PVC Application 405 (triazines ultra-violet absorbers; Ciba Specialty Chemicals Inc. makes); And add 10.1 parts VESTANAT B1358/100, so that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (B) of 1 equivalent, NCO reaches 1.0 equivalents; Further; Add 0.015 part dimethyl two neodecanoic acid tin, 9.46 parts APZ-6633, and stirred 1 hour down, obtain acrylic resin paint (i-4) at 25 ℃.
[reference example I-13]
In 100 parts aforesaid propylene acid copolymer solution (C), add 34.8 parts MIBK, 17.4 parts 2-BuOH, 112.7 parts 1-methoxyl group-2-propyl alcohol and mix, add 6.1 parts チ ヌ PVC Application 400; And add 15.6 parts デ ユ ラ ネ one ト MF-B60X (polyisocyanate compounds presoma; Asahi Chemical Industry industry (strain) is made) so that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (C) of 1 equivalent, NCO reaches 1.0 equivalents; Further; Add 0.017 part dimethyl two neodecanoic acid tin, and stirred 1 hour down, obtain acrylic resin paint (i-5) at 25 ℃.
[reference example I-14]
In 100 parts aforesaid propylene acid copolymer solution (C), add 25.4 parts MIBK, 12.7 parts 2-BuOH, 98.6 parts 1-methoxyl group-2-propyl alcohol and mix, add 4791.0 parts of (triazines ultra-violet absorbers of チ ヌ PVC Application of 4.2 parts 400,5.2 parts of チ ヌ PVC Application; 2-[2-hydroxyl-4-(1-carbonyl octyloxy ethyoxyl) phenyl]-4, two (the 4-phenyl)-1,3 of 6-; The 5-triazine, Ciba Specialty Chemicals Inc. makes), and add 10.1 parts VESTANATB1358/100; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (C) of 1 equivalent; NCO reaches 1.0 equivalents, further, adds 0.017 part dimethyl two neodecanoic acid tin, 9.41 parts APZ-6633; And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-6).
[reference example I-15]
In 100 parts aforesaid propylene acid copolymer solution (D); Add 28.6 parts MIBK, 14.3 parts 2-BuOH, 103.1 parts 1-methoxyl group-2-propyl alcohol and mix; Add 5.5 parts チ ヌ PVC Application 400, and add 12.9 parts VESTANAT B1358/100, so that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (D) of 1 equivalent; NCO reaches 1.2 equivalents; Further, add 0.026 part dimethyl two neodecanoic acid tin, 9.87 parts APZ-6633,1.64 parts チ ヌ PVC Application 123 (hindered amine light stabilizer, Ciba Specialty Chemicals Inc. makes); And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-7).
[reference example I-16]
In 100 parts aforesaid propylene acid copolymer solution (D); Add 43.0 parts MIBK, 21.5 parts 2-BuOH, 83.2 parts 1-methoxyl group-2-propyl alcohol and mix, add 4.8 parts チ ヌ PVC Application 400, and add 16.6 parts デ ユ ラ ネ one ト MF-B60X; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (D) of 1 equivalent; NCO reaches 1.0 equivalents, further, adds 0.109 part normal-butyl three (2 ethyl hexanoic acid) tin, 10.94 parts APZ-6633,4.75 parts LA-82; And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-8).
[reference example I-17]
In 100 parts aforesaid propylene acid copolymer solution (D); Add 26.5 parts MIBK, 13.2 parts 2-BuOH, 100.0 parts 1-methoxyl group-2-propyl alcohol and mix, add 5.3 parts チ ヌ PVC Application 405, and add 10.7 parts VESTANAT B1358/100; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (D) of 1 equivalent; NCO reaches 1.0 equivalents, further, adds 0.015 part dibutyl tin laurate (DBTDL), 9.55 parts APZ-6633,2.79 parts チ ヌ PVC Application 123; And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-9).
[reference example I-18]
In 100 parts aforesaid propylene acid copolymer solution (E); Add 40.6 parts MIBK, 20.3 parts 2-BuOH, 80.8 parts 1-methoxyl group-2-propyl alcohol and mix, add 5.4 parts チ ヌ PVC Application 400, and add 11.6 parts VESTANAT B1358/100; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (E) of 1 equivalent; NCO reaches 1.0 equivalents, further, adds 0.051 part normal-butyl three (2 ethyl hexanoic acid) tin, 9.66 parts APZ-6633; And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-10).
[reference example I-19]
In 100 parts aforesaid propylene acid copolymer solution (A); Add 56.3 parts MIBK, 28.1 parts 2-BuOH, 80.8 parts 1-methoxyl group-2-propyl alcohol and mix, add 6.2 parts チ ヌ PVC Application 400, and add 21.2 parts VESTANAT B1358/100; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (A) of 1 equivalent; NCO reaches 2.0 equivalents, further, adds 0.018 part dimethyl two neodecanoic acid tin; And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-11).
[reference example I-20]
In 100 parts aforesaid propylene acid copolymer solution (A); Add 26.1 parts MIBK, 13.1 parts 2-BuOH, 99.6 parts 1-methoxyl group-2-propyl alcohol and mix, add 5.3 parts チ ヌ PVC Application 400, and add 10.6 parts VESTANAT B1358/100; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (A) of 1 equivalent; NCO reaches 1.0 equivalents, further, adds 9.51 parts APZ-6633; And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-12).
[reference example I-21]
In 100 parts aforesaid propylene acid copolymer solution (C); Add 46.7 parts MIBK, 23.3 parts 2-BuOH, 87.0 parts 1-methoxyl group-2-propyl alcohol and mix, add 5.1 parts チ ヌ PVC Application 400, and add 18.7 parts デ ユ ラ ネ one ト MF-B60X; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (C) of 1 equivalent; NCO reaches 1.2 equivalents, further, adds 0.582 part normal-butyl three (2 ethyl hexanoic acid) tin, 11.64 parts APZ-6633,3.16 parts LA-82; And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-13).
[reference example I-22]
In 100 parts aforesaid propylene acid copolymer solution (B); Add 63.1 parts MIBK, 31.5 parts 2-BuOH, 103.3 parts 1-methoxyl group-2-propyl alcohol and mix, add 25.0 parts チ ヌ PVC Application 405, and add 10.1 parts VESTANAT B1358/100; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (B) of 1 equivalent; NCO reaches 1.0 equivalents, further, adds 0.015 part dimethyl two neodecanoic acid tin, 9.46 parts APZ-6633; And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-14).
[reference example I-23]
In 100 parts aforesaid propylene acid copolymer solution (F); Add 38.5 parts MIBK, 19.2 parts 2-BuOH, 78.7 parts 1-methoxyl group-2-propyl alcohol and mix, add 5.2 parts チ ヌ PVC Application 400, and add 9.6 parts VESTANAT B1358/100; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (F) of 1 equivalent; NCO reaches 1.0 equivalents, further, adds 0.015 part dimethyl two neodecanoic acid tin, 9.38 parts APZ-6633,2.72 parts LA-82; And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-15).
[reference example I-24]
In 100 parts aforesaid propylene acid copolymer solution (G); Add 63.0 parts MIBK, 31.5 parts 2-BuOH, 103.3 parts 1-methoxyl group-2-propyl alcohol and mix, add 7.0 parts チ ヌ PVC Application 405, and add 30.9 parts VESTANAT B1358/100; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic acid copolymer soln (G) of 1 equivalent; NCO reaches 1.0 equivalents, further, adds 0.021 part dibutyl tin dilaurate, 12.54 parts APZ-6633; And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-16).
[reference example I-25]
In 100 parts aforesaid propylene acid copolymer solution (H); Add 30.1 parts MIBK, 15.1 parts 2-BuOH, 70.4 parts 1-methoxyl group-2-propyl alcohol and mix; Add the チ ヌ PVC Application 123 of 4.4 parts 400,2.2 parts of チ ヌ PVC Application; And under 25 ℃, stirred 1 hour, obtain acrylic resin paint (i-17).
Figure S2007800017034D00421
Figure S2007800017034D00431
Figure S2007800017034D00441
Figure S2007800017034D00451
In addition, in table 2, each symbolic representation is following.
VEST: block polyisocyanate compound (VESTANAT B1358/100; The content ratio of the NCO that is generated is 12.4 weight %; Degussa Japan Co.; Ltd. make) デ ユ ラ ネ one ト: the xylenes/butanol solution (デ ユ ラ ネ one ト MF-B60X, Asahi Chemical Industry's industry (strain) is made) that contains the block polyisocyanate compound of 60 weight %
DMDNT: dimethyl two neodecanoic acid tin
BTEHT: monobutyl three (2 ethyl hexanoic acid) tin
DBTDL: dibutyl tin dilaurate
UVA-1: about 85% 2-{4-[(2-hydroxyl-3-dodecyloxy propyl group) oxygen]-2-hydroxy phenyl }-4, two (2, the 4-3,5-dimethylphenyl)-1 of 6-; 3,5-triazine and 2-{4-[(2-hydroxyl-3-oxygen base in three last of the ten Heavenly stems propyl group) oxygen]-2 hydroxy phenyls }-4,6-two (2; The 4-3,5-dimethylphenyl)-1; 3, the mixture of the mixture of 5-triazine and 15% 1-methoxyl group-2-propyl alcohol (チ ヌ PVC Application 400, Ciba Specialty Chemicals Inc. makes)
UVA-2:2-{4-[(2-hydroxyl-3-(2 '-ethyl) hexyl) oxygen]-2-hydroxy phenyl }-4, two (2, the 4-the 3,5-dimethylphenyl)-1,3,5-triazines of 6-(チ ヌ PVC Application 405, Ciba SpecialtyChemicals Inc. makes)
UVA-3:2-[(2-hydroxyl-4-(1-carbonyl octyloxy ethyoxyl) phenyl]-4, two (4-the phenyl)-1,3,5-triazines of 6-(チ ヌ PVC Application 479, Ciba Specialty ChemicalsInc. makes)
APZ: the ethanolic solution that contains the aminosilane coupling agent hydrolytic condensate (Ltd makes for APZ-6633, Dow Corning Toray Silicone Co.) that contains 5 weight %
HALS-1: the methacrylate (ア デ カ ス タ Block LA-82, rising sun electrochemical industry (strain) is made) that contains hindered amines photostability group
HALS-2: hindered amine light stabilizer (チ ヌ PVC Application 123, Ciba Specialty ChemicalsInc. makes)
MIBK: methyl iso-butyl ketone (MIBK)
The 2-BuOH:2-butanols
PMA:1-methoxyl group-2-propyl alcohol
(preparation of organosiloxane resins coating (ii-1)～(ii-2))
[reference example I-26]
Behind the 1M hydrochloric acid of 1.3 parts of addings in 133 parts of water-dispersion type cataloid dispersion liquids (カ タ ロ イ De SN-30, solid component concentration 30 weight %, catalyst change into industry (strain) manufacturing), fully stir.This dispersion liquid is cooled to 10 ℃, under the ice-water bath cooling, drips 162 parts of MTMSs.Begin from the dropping of MTMS, because the temperature of reaction heat mixed liquor begins to rise immediately, from dripping beginning after 5 minutes, temperature rises to 60 ℃, slowly descends through the cooling effect mixeding liquid temperature then.When mixeding liquid temperature is reduced to 30 ℃; Keep this temperature; Stirred 10 hours down at 30 ℃; Then to methanol solution that wherein to mix 0.8 part of choline concentration as curing catalysts be 45 weight %, 5 parts as the acetic acid of pH conditioning agent and 200 parts isopropyl alcohol as retarder thinner, thereby obtain organosiloxane resins coating (ii-1).
[reference example I-27]
Behind the 1M hydrochloric acid of 1 part of adding in 100 parts of water-dispersion type cataloid dispersion liquids (カ タ ロ イ De SN-30, solid component concentration 30 weight %, catalyst change into industry (strain) manufacturing), fully stir.This dispersion liquid is cooled to 10 ℃, at the ice-water bath cooling mix reagent of the dimethyldimethoxysil,ne of 158 parts of MTMSs of dropping and 3.6 parts down.Begin from the dropping of this mix reagent, because the temperature of reaction heat mixed liquor begins to rise immediately, from dripping beginning after 5 minutes, temperature rises to 60 ℃, slowly descends through the cooling effect mixeding liquid temperature then.When mixeding liquid temperature is reduced to 30 ℃; Keep this temperature; Stirred 10 hours down at 30 ℃; Then to methanol solution that wherein to mix 0.8 part of choline concentration as curing catalysts be 45 weight %, 5 parts as the acetic acid of pH conditioning agent and 200 parts isopropyl alcohol as retarder thinner, thereby obtain organosiloxane resins coating (ii-2).
(evaluation of acrylic resin paint storage stability)
[example I-1～I-9 and Comparative Example I-1]
To after three months, with the naked eye estimate the state of coating in preservation under 23 ℃ by acrylic resin paint (i-1)～(i-9) and acrylic resin paint (i-17) that reference example I-9～I-17 and reference example I-25 obtain.In addition, the coating assessment that will not observe gelation is for good.Its result is shown in Table 3.
Table 3
Acrylic resin paint No. Storage stability
Example I-1 (i-1) Well
Example I-2 (i-2) Well
Example I-3 (i-3) Well
Example I-4 (i-4) Well
Example I-5 (i-5) Well
Example I-6 (i-6) Well
Example I-7 (i-7) Well
Example I-8 (i-8) Well
Example I-9 (i-9) Well
Comparative Example I-1 (i-17) Gelation
(making of duplexer and evaluation)
According to following method duplexer is estimated.
Ocular estimate: with the naked eye confirm test piece two finishing coats outward appearance (having or not foreign matter, albefaction), have or not chap (crackle).
Connecting airtight property: cut 1mm 100 checkerboard grid at interval on the coating with the face of cutting knife in two finishing coats; Crimping NICHIBAN CO.; LTD. the adhesive tape of making (trade name: " セ ロ テ one プ " (registration mark)); And carry out vertical powerful peeling off, estimate with the quantity that residues in the checkerboard grid on the base material.
Hot water resistance: estimate cosmetic variation, the connecting airtight property of test piece being flooded the coating after 3 hours or 8 hours in boiled water.
Mar proof: according to JIS K6735; CS-10F wear ring with Calibrase society system; Carry out 1000 times Taber wear test with bear a heavy burden one side in two finishing coats of 500g; The haze value after the mensuration Taber wear test and the poor Δ H of the haze value before the Taber wear test, and estimate.Wherein, the resurfacing of wear ring (reface) uses pouncing paper S-11 to replace pouncing paper AA-400, carries out 25 times.
(haze value=Td/Tt * 100, Td: scattered light transmitance, Tt: total light transmittance)
Durability under the hot environment: test piece, is taken out test piece and estimated outward appearance, connecting airtight property after 1000 hours 100 ℃ environment held.
The environment cyclic test: with test piece the environment held 4 hours of 80 ℃ and 80%RH, the environment held 1 hour of 25 ℃ and 50%RH ,-15 ℃ environment held 4 hours, in 1 hour the circulation of environment held of 25 ℃ and 50%RH as a circulation; After carrying out such circulation 30 times repeatedly; Take out test piece, estimate outward appearance, connecting airtight property.
Weatherability: test piece need not to change ultraviolet shadow surface, and with SUGA TEST INSTRUMENTSCO., the Super Xenon Weather Meter SX-75 that LTD makes is with UV exposure intensity 180W/m 2, in 63 ℃, 120 minutes of the blackboard temperatures 18 minutes under the condition of rainfall; Carry out 3000 hours exposure test; Take out test piece; After the surface cleaned with the sponge that is soaked with neutral detergent gently, the yellow chromaticity before and after the outward appearance after the evaluation test, connecting airtight property, the test changes (Δ YI) and haze value changes (Δ H).In addition, the test piece in the exposure test was taken out once in per 500 hours, and its surface is cleaned with the sponge that is soaked with neutral detergent gently.The beam splitting type color appearance SE-2000 that makes with Japanese electric look (strain) measures yellow chromaticity (YI).
[example I-10]
Use dip coating; The acrylic resin paint (i-1) that will obtain by reference example I-9; Be coated on two surfaces of the thick polycarbonate resin of 5mm (being designated hereinafter simply as " PC resin ") sheeting; So that the thickness after the heat cure becomes 6.0 μ m, and after leaving standstill 20 minutes under 25 ℃, under 130 ℃, carry out 1 hour heat cure.Then; On the tunicle surface of this thin plate; Be coated with the organosiloxane resins coating (ii-1) that obtains by reference example I-26 with dip coating, so that the thickness after the heat cure becomes 4.0 μ m, and after leaving standstill 20 minutes under 25 ℃; Under 120 ℃, carry out 1 hour heat cure, obtain PC resin-formed body (duplexer).Each evaluation result of resulting PC resin-formed body is shown in Table 4.
[example I-11～I-22]
In the thick PC resin sheeting of 5mm,, adopt with the same method of example I-10 and make the PC resin-formed body with acrylic resin paint and the organosiloxane resins coating that table 4 is represented.Each evaluation result of resulting PC resin-formed body is shown in Table 4.
[example I-23]
According to the rear portion quarter window shape of automobile, make the thick injection-molded article of 5mm with the PC resin.On the surface of this injection-molded article, by the acrylic resin paint (i-1) that reference example I-9 obtains,, and after leaving standstill 20 minutes under 25 ℃, under 130 ℃, carry out 1 hour heat cure so that the thickness after the heat cure becomes 8.0 μ m with the dip coating coating.Then, on the tunicle surface of this thin plate, be coated with the organosiloxane resins coating (ii-2) that obtains by reference example I-27 with dip coating; So that the thickness after the heat cure becomes 4.5 μ m; And after leaving standstill 20 minutes under 25 ℃, under 120 ℃, carry out 1 hour heat cure, obtain duplexer.Each evaluation result of resulting duplexer is shown in Table 4.
[Comparative Example I-2～I-8]
In the thick PC resin sheeting of 5mm,, adopt with the same method of example I-10 and make the PC resin-formed body with acrylic resin paint shown in the table 4 and organosiloxane resins coating.Each evaluation result of resulting PC resin-formed body is shown in Table 4.
Comparative Example I-2, owing to do not use (A-2) composition in the acrylic copolymer that is adopted, therefore, the weatherability equal difference of duplexer (the Δ YI value after the atmospheric exposure test, Δ H value are greatly).
Comparative Example I-3, because the use level of (B) composition in the acrylic resin paint too much (the NCO/OH equivalent proportion is big), therefore, the connecting airtight property equal difference of the hot water resistance of duplexer.
Comparative Example I-4 does not cooperate (C) composition in the acrylic resin paint, defective appears cracking etc. in duplexer in hot water resistance.
Comparative Example I-5, because the use level of (C) composition is too much in the acrylic resin paint, therefore, the connecting airtight property equal difference at the initial stage of duplexer.
Comparative Example I-6, because the use level of (D) composition is too much in the acrylic resin paint, therefore, the connecting airtight property equal difference at the initial stage of duplexer.
Comparative Example I-7 and since employed acrylic resin paint in (A-3) components in proportions outside scope of the present invention, therefore, the connecting airtight property equal difference at the initial stage of PC resin-formed body.
Comparative Example I-8; It is the example that replaces the block polyisocyanate compound as the crosslinking agent of (B) composition with methacrylic acid trimethoxy-silylpropyl ester; The poor storage stability of this acrylic resin paint; And, use the connecting airtight property equal difference of the hot water resistance of the duplexer that this acrylic resin paint obtains.
Figure S2007800017034D00511
Figure S2007800017034D00531
[II]
(acrylate copolymer solution (A), (I's)～(N) is synthetic)
[reference example II-1]
I-1 operates equally with reference example, obtains acrylic acid copolymer soln (A).
[reference example II-2]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, adding 62.8 parts of EMA, 50.5 parts CHMA, 13.0 parts HEMA, 12.0 parts LA-82,138.2 parts MIBK and 69.1 parts 2-BuOH and also mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.33 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.6% acrylic acid copolymer soln (I).By GPC measure (post: Shodex GPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 100000.
[reference example II-3]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, adding 74.2 parts of EMA, 33.6 parts CHMA, 13.0 parts HEMA, 12.0 parts LA-82,132.8 parts MIBK and 66.4 parts 2-BuOH and also mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.33 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.5% acrylic acid copolymer soln (J).By GPC measure (post: Shodex GPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 95000.
[reference example II-4]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, adding 68.5 parts of EMA, 42.1 parts CHMA, 13.0 parts HEMA, 12.0 parts LA-82,135.5 parts MIBK and 67.8 parts 2-BuOH and also mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.33 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.6% acrylic acid copolymer soln (K).By GPC measure (post: Shodex GPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 100000.
[reference example II-5]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement; Adding 59.4 parts of EMA, 50.5 parts CHMA, 13.0 parts HEMA, 12.0 parts LA-82,22.2 parts MOI-T405 (the addition reaction product of methacrylic acid 2-ethyl isocyanate, Tinuvin405 and カ レ Application ズ MOI clear and that electrician's (strain) makes), 160.4 parts MIBK and 80.2 parts 2-BuOH also mixes.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.34 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.5% acrylic acid copolymer soln (L).By GPC measure (post: Shodex GPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 85000.
[reference example II-6]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, adding 102.7 parts of EMA, 13.0 parts HEMA, 115.7 parts MIBK and 57.9 parts 2-BuOH and also mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.33 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.6% acrylic acid copolymer soln (M).By GPC measure (post: ShodexGPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 130000.
[reference example II-7]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, adding 57.1 parts of EMA, 33.6 parts CHMA, 32.5 parts HEMA, 12.0 parts LA-82,123.3 parts MIBK and 61.6 parts 2-BuOH and also mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.33 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.08 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, obtain non-volatile part of concentration and be 39.7% acrylic acid copolymer soln (N).By GPC measure (post: Shodex GPCA-804, elutriant: chloroform) and the weight average molecular weight that is converted into the acrylic copolymer of polystyrene be 135000.
In addition, the MOI-T405 that in reference example II-5, uses is synthetic through following method.
[MOI-T405's is synthetic]
In the flask that has reflux condenser and agitating device; Add 443.4 parts 126.6 parts, 350.3 parts of methyl iso-butyl ketone (MIBK)s (being designated hereinafter simply as " MIBK ") 405,93.1 parts of チ ヌ PVC Application methacrylic acid 2-ethyl isocyanate and mix, be heated to 80 ℃.Then, add 0.1 part dibutyl tin dilaurate, stirred 30 minutes down synthermal.After being cooled to room temperature, resulting solution is transferred in the water, after the stirring, with MIBK abstraction reaction thing.The grease that distillation removal MIBK is obtained drips to methyl alcohol, stirs and obtains pale yellow powder.Dry this powder has obtained 2-methacryloxyethyl carbamic acid 1-{3-hydroxyl-4-[4, two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines-2-yls of 6-] phenoxy group }-3-(2-ethyl hexyl oxy)-2-propyl group (being designated hereinafter simply as " MOI-405 ").
Figure S2007800017034D00581
In addition, in table 5, following material of each symbolic representation or the expression material identical with table 1.
MOI-T405: the addition reaction product of methacrylic acid 2-ethyl isocyanate, Tinuvin405 and clear and electrician's (strain) manufacturing カ レ Application ズ MOI (representing) with following formula
Figure S2007800017034D00591
AIBN1: the azodiisobutyronitrile that adds for the first time
AIBN2: the azodiisobutyronitrile that adds for the second time
(preparation of acrylic acid resin composition (i-18)～(i-26))
[reference example II-8]
In 100 parts aforesaid propylene acid copolymer solution (A), add 39.2 parts MIBK, 19.6 parts 2-BuOH, 79.5 parts 1-methoxyl group-2-propyl alcohol (being designated hereinafter simply as " PMA ") and mix, add 5.3 parts チ ヌ PVC Application 400 (triazines ultra-violet absorbers; Ciba SpecialtyChemicals Inc. makes); And add 10.6 parts VESTANAT B1358/100 (Ltd. makes for polyisocyanate compounds presoma, Degussa Japan Co.); So that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (A) of 1 equivalent; NCO reaches 1.0 equivalents, further, adds 9.5 parts the APZ-6633 (ethanolic solution of silane coupling agent hydrolytic condensate; Solid constituent is 5 weight %; Nippon Unicar Company Limited makes), 0.015 part dimethyl two neodecanoic acid tin (being designated hereinafter simply as " DMDNT "), and stirred 1 hour down at 25 ℃, obtain acrylic acid resin composition (i-18).Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
[reference example II-9]
In 100 parts aforesaid propylene acid copolymer solution (I); Add 38.2 parts MIBK, 19.1 parts 2-BuOH, 78.5 parts PMA and mix; Add the チ ヌ PVC Application 479 of 4.2 parts 400,1.0 parts of チ ヌ PVC Application, and add 9.7 parts VESTANAT B1358/100, so that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (I) of 1 equivalent; NCO reaches 1.0 equivalents; Add 9.4 parts APZ-6633,0.015 part DMDNT, and stirred 1 hour down, obtain acrylic acid resin composition (i-19) at 25 ℃.Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
[reference example II-10]
In 100 parts aforesaid propylene acid copolymer solution (J); Add 43.2 parts MIBK, 21.6 parts 2-BuOH, 83.6 parts PMA and mix; Add 8.3 parts チ ヌ PVC Application 400, and add 10.1 parts VESTANAT B1358/100, so that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (J) of 1 equivalent; NCO reaches 1.0 equivalents; Add 9.4 parts APZ-6633,0.05 minute normal-butyl three (2 ethyl hexanoic acid) tin (BTEHT), and stirred 1 hour down, obtain acrylic acid resin composition (i-20) at 25 ℃.Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
[reference example II-11]
In 100 parts aforesaid propylene acid copolymer solution (K); Add 44.1 parts MIBK, 20.1 parts 2-BuOH, 80.5 parts PMA and mix, add the チ ヌ PVC Application 405 of 4.8 parts 400,1.6 parts of チ ヌ PVC Application, and add 9.9 parts VESTANAT B1358/100; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (K) of 1 equivalent; NCO reaches 1.0 equivalents, further, adds 0.025 part DMDNT; And under 25 ℃, stirred 1 hour, obtain acrylic acid resin composition (i-21).Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
[reference example II-12]
In 100 parts aforesaid propylene acid copolymer solution (L); Add 29.3 parts MIBK, 22.1 parts 2-BuOH, 84.0 parts PMA and mix, add 9.5 parts VESTANATB1358/100, so that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (L) of 1 equivalent; NCO reaches 1.0 equivalents; Add 9.3 parts APZ-6633,0.025 part DMDNT, and stirred 1 hour down, obtain acrylic acid resin composition (i-22) at 25 ℃.Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
[reference example II-13]
In 100 parts aforesaid propylene acid copolymer solution (M); Add 40.4 parts MIBK, 20.2 parts 2-BuOH, 80.7 parts PMA and mix; Add 5.4 parts チ ヌ PVC Application 400, and add 11.6 parts VESTANAT B1358/100, so that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (M) of 1 equivalent; NCO reaches 1.0 equivalents; Add 9.7 parts APZ-6633,0.051 part BTEHT, and stirred 1 hour down, obtain acrylic acid resin composition (i-23) at 25 ℃.Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
[reference example II-14]
In 100 parts aforesaid propylene acid copolymer solution (N); Add 67.4 parts MIBK, 33.7 parts 2-BuOH, 107.6 parts PMA and mix; Add 8.8 parts チ ヌ PVC Application 405, and add 32.6 parts VESTANAT B1358/100, so that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (N) of 1 equivalent; NCO reaches 1.0 equivalents; Add 12.8 parts APZ-6633,0.072 part BTEHT, and stirred 1 hour down, obtain acrylic acid resin composition (i-24) at 25 ℃.Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
[reference example II-15]
In 100 parts aforesaid propylene acid copolymer solution (J); Add 43.8 parts MIBK, 21.9 parts 2-BuOH, 84.2 parts PMA and mix, adds 15.7 parts チ ヌ PVC Application 329 (benzotriazole ultra-violet absorber, Ciba Specialty Chemicals Inc. manufacturing); And add 10.1 parts VESTANAT B1358/100; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (J) of 1 equivalent, NCO reaches 1.0 equivalents, adds 9.4 parts APZ-6633,0.02 part DMDNT; And under 25 ℃, stirred 1 hour, obtain acrylic acid resin composition (i-25).Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
[reference example II-16]
In 100 parts aforesaid propylene acid copolymer solution (J); Add 41.3 parts MIBK, 20.6 parts 2-BuOH, 81.6 parts PMA and mix, and add 10.1 parts VESTANATB1358/100, so that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (J) of 1 equivalent; NCO reaches 1.0 equivalents; Add 9.4 parts APZ-6633,0.02 part DMDNT, and stirred 1 hour down, obtain acrylic acid resin composition (i-26) at 25 ℃.Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
Figure S2007800017034D00631
In table 6, following material of each symbolic representation or the expression material identical with table 2.
UVA-4:2-(2H-BTA-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol (チ ヌ PVC Application 329, Ciba Specialty Chemicals Inc. makes)
(preparation of organosiloxane resins coating (ii-3)～(ii-5))
[reference example II-17]
Behind the 1M hydrochloric acid of 1.3 parts of addings in 133 parts of water-dispersion type cataloid dispersion liquids (カ タ ロ イ De SN-30, solid component concentration 30 weight %, catalyst change into industry (strain) manufacturing), fully stir.This dispersion liquid is cooled to 10 ℃, under the ice-water bath cooling, drips 216 parts of MTMSs.Begin from the dropping of MTMS, because the temperature of reaction heat mixed liquor begins to rise immediately, from dripping beginning after 5 minutes, temperature rises to 60 ℃, slowly descends through the cooling effect mixeding liquid temperature then.When mixeding liquid temperature is reduced to 30 ℃; Keep this temperature; Stirred 10 hours down at 30 ℃, then to methanol solution that wherein to mix 1.1 parts of choline concentrations as curing catalysts be 45 weight %, 6.7 parts as the acetic acid of pH conditioning agent and 220 parts isopropyl alcohol as retarder thinner, further add 6.8 parts 710T (IPA decentralized titanium oxide dispersion liquid; TAYCACORPORATION makes), thus organosiloxane resins coating (ii-3) obtained.
[reference example II-18]
Behind the 1M hydrochloric acid of 1 part of adding in 133 parts of water-dispersion type cataloid dispersion liquids (カ タ ロ イ De SN-30, solid component concentration 30 weight %, catalyst change into industry (strain) manufacturing), fully stir.This dispersion liquid is cooled to 10 ℃, at the ice-water bath cooling mix reagent of the dimethyldimethoxysil,ne of 208.8 parts of MTMSs of dropping and 4.7 parts down.Begin from the dropping of this mix reagent, because the temperature of reaction heat mixed liquor begins to rise immediately, from dripping beginning after 5 minutes, temperature rises to 60 ℃, slowly descends through the cooling effect mixeding liquid temperature then.When mixeding liquid temperature is reduced to 30 ℃; Keep this temperature; Stirred 10 hours down at 30 ℃; Then to methanol solution that wherein to mix 1.1 parts of choline concentrations as curing catalysts be 45 weight %, 6.7 parts as the acetic acid of pH conditioning agent and 210 parts isopropyl alcohol as retarder thinner, further add 6.7 parts 710T, thereby obtain organosiloxane resins coating (ii-4).
[reference example II-19]
Behind the 1M hydrochloric acid of 1.3 parts of addings in 133 parts of water-dispersion type cataloid dispersion liquids (カ タ ロ イ De SN-30, solid component concentration 30 weight %, catalyst change into industry (strain) manufacturing), fully stir.This dispersion liquid is cooled to 10 ℃, under the ice-water bath cooling, drips 216 parts of MTMSs.Begin from the dropping of MTMS, because the temperature of reaction heat mixed liquor begins to rise immediately, from dripping beginning after 5 minutes, temperature rises to 60 ℃, slowly descends through the cooling effect mixeding liquid temperature then.When mixeding liquid temperature is reduced to 30 ℃; Keep this temperature; Stirred 10 hours down at 30 ℃; Then to methanol solution that wherein to mix 1.1 parts of choline concentrations as curing catalysts be 45 weight %, 6.7 parts as the acetic acid of pH conditioning agent and 220 parts isopropyl alcohol as retarder thinner, thereby obtain organosiloxane resins coating (ii-5).
Figure S2007800017034D00671
In table 7, each symbolic representation is following.
(E composition)
SN-30: カ タ ロ イ De SN-30 (water-dispersion type cataloid, solid component concentration 30 weight %, catalyst change into industry (strain) manufacturing)
(F composition)
MTMOS: MTMS
DMDMOS: dimethyldimethoxysil,ne
(G composition)
710T:IPA decentralized titanium oxide dispersion liquid, TAYCA CORPORATION makes (solid component content: 42.5 weight %)
(making of duplexer and evaluation)
Carry out the evaluation of duplexer with following method.In addition, then adopt the evaluation method identical to carry out to outward appearance, connecting airtight property and hot water resistance with above-mentioned [I].Wherein, hot water resistance is a dipping 3 hours and estimate in boiled water.
The conservation rate of light absorpting ability: on a surface of the thick glass plate of 1mm; Any one in acrylic resins of painting solution or the organosiloxane resins composite paint only; So that the thickness after the heat cure becomes 1 μ m, and measure the absorbance of filming under wavelength 300nm with the spectrophotometer U-3100 that (strain) Hitachi makes.With this moment absorbance, when being coated with acrylic resin soln as P (Abs 0), when being coated with the organosiloxane resins composite paint as T (Abs 0).To the coated face of this duplexer, with SUGA TEST INSTRUMENTS CO., the SuperXenon Weather Meter SX-75 that LTD makes is with UV exposure intensity 180W/m 2, under 63 ℃ of the blackboard temperatures, carry out 500 hours exposure test after, measure the absorbance of filming under the wavelength 300nm.Absorbance after this is exposed to the open air, when being coated with acrylic resin soln as P (Abs), when being coated with the organosiloxane resins composite paint as T (Abs).Obtain the conservation rate (%) of light absorpting ability with following formula.
When being coated with rete: P (Abs)/P (Abs for acrylic resin 0) * 100 (%)
When filming: T (Abs)/T (Abs for organosiloxane resins 0) * 100 (%)
The transparency: the difference Δ H of haze value that obtains haze value and the polycarbonate resin laminate behind the range upon range of ground floor and the second layer of polycarbonate resin thin plate.Haze value then adopts integrating sphere type mist shadow appearance, and measures according to JIS K6735.
(haze value=Td/Tt * 100, Td: scattered beam transmitance, Tt: total light transmittance)
Mar proof: according to JIS K6735; CS-10F (TYPE IV) wear ring with Calibrase society system; Carry out 500 times Taber wear test with bear a heavy burden one side in two finishing coats of 500g; The haze value after the mensuration Taber wear test and the poor Δ H of the haze value before the Taber wear test, and estimate.
Weatherability: as ultraviolet shadow surface, with SUGA TESTINSTRUMENTS CO., the Super Xenon Weather Meter SX-75 that LTD makes is with UV exposure intensity 180W/m with the one side of test piece 2, in 63 ℃, 120 minutes of the blackboard temperatures 18 minutes be under the condition of raining, carry out 3000 hours exposure test, take out test piece, the outward appearance after the evaluation test, connecting airtight property, the difference Δ H and the yellow chromaticity changes delta YI of the haze value before and after the test.Yellow chromaticity (YI) is then measured through the beam splitting type color appearance SE-2000 that Japanese electric look (strain) is made.
[example II-1]
Use dip coating; The acrylic acid resin composition (i-18) that will obtain by reference example II-9; Be coated on two surfaces of the thick polycarbonate resin of 5mm (being designated hereinafter simply as " PC resin ") sheeting; So that the thickness after the heat cure becomes 10.0 μ m, and after leaving standstill 20 minutes under 25 ℃, under 130 ℃, carry out 1 hour heat cure.Then; On the tunicle surface of this thin plate; Be coated with the organosiloxane resins coating (ii-3) that obtains by reference example II-17 with dip coating, so that the thickness after the heat cure becomes 4.5 μ m, and after leaving standstill 20 minutes under 25 ℃; Under 125 ℃, carry out 1 hour heat cure, obtain PC resin-formed body (duplexer).The formation of resulting PC laminated resin body is shown in Table 8, each evaluation result is shown in Table 9.
[example II-2～II-9]
In the thick PC resin sheeting of 5mm, acrylic acid resin composition and organosiloxane resins coating with table 8 is represented according to the thickness of table 8 expression, adopt with the same method of example II-1 and make duplexer.Each evaluation result of resulting duplexer is shown in Table 9.
[Comparative Example I I-1～II-4]
In the thick PC resin sheeting of 5mm, acrylic acid resin composition and organosiloxane resins coating with table 8 is represented according to the thickness of table 8 expression, adopt with the same method of example II-1 and make duplexer.Each evaluation result of resulting duplexer is shown in Table 9.
Figure S2007800017034D00701
Figure S2007800017034D00711
Figure S2007800017034D00721
Figure S2007800017034D00731
[III]
[reference example III-1] (preparation of acrylic resin paint)
Adopt with the same method of reference example I-1 and obtained acrylic acid copolymer soln (A).In this acrylic acid copolymer soln (A) of 100 parts, add 43.2 parts MIBK, 21.6 parts 2-BuOH, 83.5 parts 1-methoxyl group-2-propyl alcohol and mix, then; Add 5.3 parts チ ヌ PVC Application 400 (triazines ultra-violet absorber, Ciba Specialty Chemicals Inc. makes), and add 10.6 parts VESTANAT B1358/100 (polyisocyanate compounds presoma; Degussa Japan Co.; Ltd. make) so that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (A) of 1 equivalent, NCO reaches 1.0 equivalents; Further; Add 0.015 part dimethyl two neodecanoic acid tin, and stirred 1 hour down, obtain acrylic acid resin composition (i-27) at 25 ℃.
[reference example III-2] (preparation of organosiloxane resins stoste)
Behind the concentrated hydrochloric acid (12M) of 0.1 part of adding in 100 parts of water-dispersion type cataloid dispersion liquids (カ タ ロ イ De SN-30, solid component concentration 30 weight %, catalyst change into industry (strain) manufacturing), fully stir.This dispersion liquid is cooled to 10 ℃, to wherein dripping 161 parts of MTMSs.Begin from the dropping of MTMS, because the temperature of reaction heat mixed liquor begins to rise immediately, from dripping after MTMS begins a few minutes, temperature rises to 60 ℃.After reaching 60 ℃, cool off with ice-water bath reacting liquid temperature is slowly descended.When mixeding liquid temperature is reduced to 35 ℃; Keep this temperature; Stirred 5 hours down at 30 ℃,, thereby obtain organosiloxane resins stoste (α) then to wherein mixing 0.8 part of choline methanol solution, 5 parts of acetic acid of 45% as the pH conditioning agent as curing catalysts.
[reference example III-3]
Be added drop-wise to except mix reagent the dimethyldimethoxysil,ne of 156.8 parts MTMS and 3.5 parts 100 parts interpolation the water-dispersion type cataloid dispersion liquid of 0.1 part of concentrated hydrochloric acid (12M) (カ タ ロ イ De SN-30; Solid component concentration 30 weight %; Catalyst changes into industry (strain) manufacturing) in addition; Adopt the preparation method identical, obtain organosiloxane resins stoste (β) with reference example III-2.
[reference example III-4]
Except 156.5 parts MTMS, 3.5 parts the mix reagent of 2-hydroxyl-4-(3-triethoxysilyl propoxyl group) benzophenone of dimethyldimethoxysil,ne and 0.76 part are added drop-wise to 100 parts interpolation the water-dispersion type cataloid dispersion liquid of 0.1 part of concentrated hydrochloric acid (12M) (カ タ ロ イ De SN-30; Solid component concentration 30 weight %; Catalyst changes into industry (strain) manufacturing) in addition; Adopt and the identical preparation method of reference example III-2, obtain organosiloxane resins stoste (γ).
(making of duplexer and evaluation)
Carry out the evaluation of duplexer with following method.In addition, then adopt the evaluation method identical to carry out to outward appearance, connecting airtight property and hot water resistance with above-mentioned [I].Wherein, hot water resistance is a dipping 3 hours and estimate in boiled water.
The particle size distribution of metal oxide particle:, measure the particle of 3～6000nm particle size range with the particle size distribution device (マ イ Network ロ ト ラ Star Network UPA-ST150, a day machine dress (strain) is made) of laser diffraction formula.In this particle size distribution, expression is equivalent to from particulate side accumulation 50%, the particle diameter D50 of accumulation 90%, the numerical value (volume reference) of D90.And, according to above-mentioned numerical value, calculate the ratio of D90/D50 respectively.
Haze value is estimated: from the plastic basis material before two finishing coats and the coating; Cut out the square that the length of side is 50mm; With Japanese electric look system nephelometer NDH 2000 haze value difference Δ H (the Δ H=H1-H2 of Industrial Co., Ltd to them; H1: the haze value of two finishing coats, H2: the haze value of the plastic basis material before the coating) estimate (JIS K7136).
(haze value=Td/Tt * 100, Td: scattered beam transmitance, Tt: total light transmittance)
Mar proof: according to JIS K6735; CS-10F wear ring with Calibrase society system; Carry out 500 times Taber wear test with bear a heavy burden one side in two finishing coats of 500g; The haze value after the mensuration Taber wear test and the poor Δ H of the haze value before the Taber wear test, and estimate.Wherein, the resurfacing of wear ring (reface) uses pouncing paper AA-400, carries out 25 times.
(haze value=Td/Tt * 100, Td: scattered light transmitance, Tt: total light transmittance)
Weatherability: need not to change the ultraviolet shadow surface of test piece, with SUGA TEST INSTRUMENTSCO., the Super Xenon Weather Meter SX-75 that LTD makes is with UV exposure intensity 180W/m 2, in 63 ℃, 120 minutes of the blackboard temperatures 18 minutes be under the condition of raining; Carry out 2000 hours exposure test, take out test piece, after the surface is cleaned with the sponge that is soaked with neutral detergent gently; Estimate outward appearance, connecting airtight property, the yellow chromaticity before and after the test changes (Δ YI).In addition, the test piece in the exposure test was taken out once in per 500 hours, and its surface is cleaned with the sponge that is soaked with neutral detergent gently.Yellow chromaticity (YI) is then measured through the beam splitting type color appearance SE-2000 that Japanese electric look (strain) is made.
[EXAMPLE III-1]
With the 2-propyl alcohol dilution of 13g titanium oxide slurries (TAYCACORPORATION makes for 710T, solid component concentration 40～45 weight %) with 870g.These slurries are carried out dispersion treatment with bead mill (ウ Le ト ラ ア ペ Star Network ス ミ Le UAM-015, longevity industry (strain) is made).Dispersion treatment is carrying out these slurries through the mode of 3 UAM-015, wherein, this UAM-015 is filled with the ZrO of Φ 0.03mm 2Pearl.Accumulation 50% particle diameter of these slurries in the laser diffractometry particle size distribution is respectively 18nm and 56nm with the particle diameter of accumulation 90%.Then, drip 267 parts organosiloxane resins stoste (α) to these slurries of 177 parts, and fully stir, thereby obtain organosiloxane resins coating (ii-6).The ratio of components of the detailed composition of coating (ii-6) is shown in Table 10.In advance use dip coating,, become 8 μ m so that solidify thickness, and under 130 ℃, carry out 1 hour heat cure, thereby prepare the thick Merlon thin plate of transparent 5mm at two surface coated acrylic resin paints (i-27) of Merlon sheeting.On two surfaces of the thick Merlon thin plate of this transparent 5mm, be coated with above-mentioned coating (ii-6) with dip coating, become 4 μ m so that solidify thickness, and under 125 ℃, carry out 1 hour heat cure, thus the duplexer that obtains having coating.To be shown in Table 11 resulting evaluation result with duplexer of coating.
[EXAMPLE III-2]
With the 2-propyl alcohol dilution of 26g titanium oxide slurries (TAYCACORPORATION makes for 710T, solid component concentration 40～45 weight %) with 884g.Likewise use bead mill (ウ Le ト ラ ア ペ Star Network ス ミ Le UAM-015, longevity industry (strain) is made) to carry out dispersion treatment to these slurries and EXAMPLE III-1.Accumulation 50% particle diameter of these slurries in the laser diffractometry particle size distribution is respectively 31nm and 63nm with the particle diameter of accumulation 90%.Then, drip 266 parts organosiloxane resins stoste (β) to these slurries of 182 parts, and fully stir, thereby obtain organosiloxane resins coating (ii-7).The ratio of components of the detailed composition of coating (ii-7) is shown in Table 10.Except using this coating (ii-7), adopt and the identical rubbing method of EXAMPLE III-1 the range upon range of body of transparent Merlon that obtains having coating.To the evaluation result of resulting duplexer be shown in Table 11.
[EXAMPLE III-3]
With the 2-propyl alcohol dilution of 56g titanium oxide slurries (Osaka, Sumitomo cement (strain) is made for PCTR-2020, solid component concentration 20 weight %) with 848g.Likewise use bead mill (ウ Le ト ラ ア ペ Star Network ス ミ Le UAM-015, longevity industry (strain) is made) to carry out dispersion treatment to these slurries and EXAMPLE III-1.Accumulation 50% particle diameter of these slurries in the laser diffractometry particle size distribution is respectively 44nm and 75nm with the particle diameter of accumulation 90%.Then, drip 267 parts organosiloxane resins stoste (α) to these slurries of 181 parts, and fully stir, thereby obtain organosiloxane resins coating (ii-8).The ratio of components of the detailed composition of coating (ii-8) is shown in Table 10.Except using this coating (ii-8), adopt and the identical rubbing method of EXAMPLE III-1 the range upon range of body of transparent Merlon that obtains having coating.To the evaluation result of resulting duplexer be shown in Table 11.
[EXAMPLE III-4]
With the 2-propyl alcohol dilution of 93g titanium oxide slurries (TAYCACORPORATION makes for 710T, solid component concentration 40～45 weight %) with 930g.Likewise use bead mill (ウ Le ト ラ ア ペ Star Network ス ミ Le UAM-015, longevity industry (strain) is made) to carry out dispersion treatment to these slurries and EXAMPLE III-1.Accumulation 50% particle diameter of these slurries in the laser diffractometry particle size distribution is respectively 21nm and 66nm with the particle diameter of accumulation 90%.Then, drip 267 parts organosiloxane resins stoste (γ) to these slurries of 203 parts, and fully stir, thereby obtain organosiloxane resins coating (ii-9).The ratio of components of the detailed composition of coating (ii-9) is shown in Table 10.Except using this coating (ii-9), adopt and the identical rubbing method of EXAMPLE III-1 duplexer that obtains having coating.To the evaluation result of resulting duplexer be shown in Table 11.
[Comparative Example I II-1]
With the 2-propyl alcohol dilution of 254g titanium oxide slurries (TAYCACORPORATION makes for 710T, solid component concentration 40～45 weight %) with 1050g.Likewise use bead mill (ウ Le ト ラ ア ペ Star Network ス ミ Le UAM-015, longevity industry (strain) is made) to carry out dispersion treatment to these slurries and EXAMPLE III-1.Accumulation 50% particle diameter of these slurries in the laser diffractometry particle size distribution is respectively 42nm and 72nm with the particle diameter of accumulation 90%.Then, use coating with coating stoste (γ) to the second layer of 267 parts of these slurries droppings of 261 parts, and fully stir, thereby obtain the second layer with being coated with coating (ii-10).The ratio of components of the detailed composition of coating (ii-10) is shown in Table 10.Except using this coating (ii-10), adopt and the identical rubbing method of EXAMPLE III-1, obtain duplexer.To the evaluation result of resulting duplexer be shown in Table 11.
Figure S2007800017034D00791
Each symbolic representation is following in table 10.
(1) SN30: water-dispersion type cataloid dispersion liquid (カ タ ロ イ De SN30, solid component concentration 30 weight %, average grain diameter 17～20nm, catalyst change into industry (strain) manufacturing)
(2) MTMOS: MTMS
(3) DMDMOS: dimethyldimethoxysil,ne
(4) contain the alkoxy silane (azmax (strain) makes for SIH6200,2-hydroxyl-4-(3-triethoxysilyl propoxyl group) benzophenone) of UV absorbing group
(5) 710T: the titanium oxide slurries (710T, solid component concentration 40～45 weight %, 2-propyl alcohol decentralized, TAYCA CORPORATION makes)
(6) PCTR-2020: titanium oxide slurries (Osaka, Sumitomo cement (strain) is made for PCTR-2020, solid component concentration 20 weight %)
(7) TTO-V-3: expression titanium dioxide powder (TTO-V-3, the former industry of stone (strain) is made), expression cataloid and metal oxide only have the weight portion of solid constituent, and the weight portion of MTMS representes to be converted into CH 3SiO 3/2Numerical value, the weight portion of dimethyldimethoxysil,ne representes to be converted into (CH 3) 2The numerical value of SiO, the weight portion that contains the alkoxy silane of UV absorbing group representes to be converted into the numerical value of hydrolytic condensate.
Figure S2007800017034D00811
In table 11, letter is represented as follows respectively.
(1) a: with respect to the match ratio (weight %) of metal oxide (c) composition of hydrolytic condensate (b composition) total amount of cataloid (a composition) and alkoxy silane
And, in table 11, the following material of each symbolic representation.
(2) D50: accumulation 50% particle diameter (volume reference) of metal oxide in the laser diffractometry particle size distribution
(3) D90: accumulation 90% particle diameter (volume reference) of metal oxide in the laser diffractometry particle size distribution
[IV]
(methacrylate synthetic) with triazines ultra-violet absorber residue
[reference example IV-1]
Adopt and above-mentioned [MOI-T405's is synthetic] identical method; Obtained 2-methacryloxyethyl carbamic acid 1-{3-hydroxyl-4-[4, two (2, the 4-3,5-dimethylphenyl)-1 of 6-; 3,5-triazine-2-yl] phenoxy group }-3-(2-ethyl hexyl oxy)-2-propyl group (being designated hereinafter simply as " MOI-405 ").
(synthesizing of acrylic acid copolymer soln (I)～(V))
[reference example IV-2]
Have reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, adding 37.2 parts EMA (being designated hereinafter simply as " EMA "), 201.9 parts cyclohexyl methacrylate (being designated hereinafter simply as " CHMA "), 26.0 parts 2-hydroxyethyl methacrylate (being designated hereinafter simply as " HEMA "), 54.7 parts the MOI-T405 that obtains by reference example IV-1,47.9 parts the LA-82 (methacrylate that contains hindered amines photostability group; Methacrylic acid 1,2,2,6,6-pentamethyl-4-piperidines ester, rising sun electrochemical industry (strain) is made), 551.5 parts MIBK and mixing.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.66 part azodiisobutyronitrile (being designated hereinafter simply as " AIBN "), in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.16 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, be cooled near the room temperature after, adds 275.8 parts 2-butanols (being designated hereinafter simply as " 2-BuOH "), obtain non-volatile part concentration and be 30.5% acrylic acid copolymer soln (I).
[reference example IV-3]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, add 62.1 parts EMA, 168.2 parts CHMA, 26.0 parts HEMA, 41.4 parts the MOI-T405 that obtains by reference example 1,47.9 parts LA-82,518.4 parts MIBK and mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.66 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.16 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, be cooled near the room temperature after, adds 259.2 parts of 2-BuOH, obtain non-volatile part concentration and be 30.4% acrylic acid copolymer soln (II).
[reference example IV-4]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, add 83.6 parts EMA, 168.2 parts CHMA, 26.0 parts HEMA, 50.3 parts the MOI-T405 that obtains by reference example 1,492.1 parts MIBK and mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.66 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.16 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, be cooled near the room temperature after, adds 246.1 parts of 2-BuOH, obtain non-volatile part concentration and be 30.5% acrylic acid copolymer soln (III).
[reference example IV-5]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, add 48.9 parts EMA, 201.9 parts CHMA, 26.0 parts HEMA, 53.2 parts the MOI-T405 that obtains by reference example 1,23.9 parts LA-82,530.9 parts MIBK and mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.66 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.16 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, be cooled near the room temperature after, adds 265.4 parts of 2-BuOH, obtain non-volatile part concentration and be 30.4% acrylic acid copolymer soln (IV).
[reference example IV-6]
Having reflux condenser and agitating device and carrying out in the flask of nitrogen replacement, add 205.5 parts EMA, 26.0 parts HEMA, 347.2 parts MIBK and mix.In mixture, lead to 15 minutes nitrogen and after carrying out deoxidation, under stream of nitrogen gas, be warming up to 70 ℃, add 0.66 part AIBN, in stream of nitrogen gas, 70 ℃ of following stirrings made it to react in 5 hours.Further, add 0.16 part AIBN, and be warming up to 80 ℃ and make it to react 3 hours, be cooled near the room temperature after, adds 173.6 parts of 2-BuOH, obtain non-volatile part concentration and be 30.6% acrylic acid copolymer soln (V).
Figure S2007800017034D00851
In table 12, the material that each symbolic representation is identical with table 1 or table 5.
(preparation of acrylic acid resin composition (i-28)～(i-32))
[reference example IV-7]
In 100 parts aforesaid propylene acid copolymer solution (I), add 18.6 parts MIBK, 9.3 parts 2-BuOH, 64.9 parts 1-methoxyl group-2-propyl alcohol (being designated hereinafter simply as " PMA ") and mix, and add 10.6 parts VESTANAT B1358/100 (block polyisocyanate compound; Degussa Japan Co., Ltd. makes) so that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (I) of 1 equivalent; NCO reaches 1.0 equivalents; Further, (ethanolic solution of silane coupling agent hydrolytic condensate, solid constituent are 5 weight % to add 5.6 parts APZ-6633; Dow Corning Toray Co.; Ltd makes), 0.011 part dibutyl tin dilaurate, and stirred 1 hour down at 25 ℃, obtain acrylic acid resin composition (i-28).Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
[reference example IV-8]
In 100 parts aforesaid propylene acid copolymer solution (II); Add 18.8 parts MIBK, 9.4 parts 2-BuOH, 65.2 parts PMA and mix, and add 6.0 parts VESTANATB1358/100, so that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (II) of 1 equivalent; NCO reaches 1.0 equivalents; Further, add 0.53 part Tinuvin479 (triazines ultra-violet absorber, Ciba Specialty Chemicals Inc. make), 7.0 parts of APZ-6633,0.011 part dimethyl two neodecanoic acid tin (being designated hereinafter simply as " DMDNT "); And under 25 ℃, stirred 1 hour, obtain acrylic acid resin composition (i-29).Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
[reference example IV-9]
In 100 parts aforesaid propylene acid copolymer solution (III), add 19.5 parts MIBK, 9.7 parts 2-BuOH, 65.8 parts PMA and mix, and add 6.3 parts VESTANATB1358/100; So that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (III) of 1 equivalent; NCO reaches 1.0 equivalents, further, adds 7.0 parts of APZ-6633,0.018 part DMDNT; And under 25 ℃, stirred 1 hour, obtain acrylic acid resin composition (i-30).Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
[reference example IV-10]
In 100 parts aforesaid propylene acid copolymer solution (IV); Add 7.8 parts MIBK, 3.9 parts 2-BuOH, 81.3 parts PMA and mix; And add 5.9 parts VESTANATB1358/100, so that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (IV) of 1 equivalent, NCO reaches 1.0 equivalents; Further; Add 0.036 part normal-butyl three (2 ethyl hexanoic acid) tin (being designated hereinafter simply as " BTEHT "), and stirred 1 hour down, obtain acrylic acid resin composition (i-31) at 25 ℃.Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
[reference example IV-11]
In 100 parts aforesaid propylene acid copolymer solution (V); Add 23.2 parts MIBK, 11.6 parts 2-BuOH, 69.5 parts PMA and mix, and add 9.0 parts VESTANATB1358/100, so that with respect to the hydroxyl of the acrylic copolymer in the acrylic resin soln (V) of 1 equivalent; NCO reaches 1.0 equivalents; Further, add 4.1 parts Tinuvin400 (triazines ultra-violet absorber, Ciba Specialty Chemicals Inc. make), 7.5 parts APZ-6633,0.040 part BTEHT; And under 25 ℃, stirred 1 hour, obtain acrylic acid resin composition (i-32).Resulting acrylic acid resin composition after preserving three months under 23 ℃, is with the naked eye estimated outward appearance, and its result does not observe gelation, and storage stability is good.
Figure S2007800017034D00881
In table 13, the material that each symbolic representation is identical with table 2.
(preparation of organosiloxane resins coating (ii-11)～(ii-12))
[reference example IV-12]
Behind the 1M hydrochloric acid of 1.3 parts of addings in 133 parts the water-dispersion type cataloid dispersion liquids (カ タ ロ イ De SN-30, solid component concentration 30 weight %, catalyst change into industry (strain) manufacturing), fully stir.This dispersion liquid is cooled to 10 ℃, under the ice-water bath cooling, drips 216 parts MTMS.After the dropping of MTMS finishes; Stirred 10 hours down at 30 ℃; Then to wherein mixing 1.1 parts of choline methanol solutions (content of choline is 45 weight %), 6.7 parts acetic acid and 220 parts isopropyl alcohol as retarder thinner as curing catalysts; Further add 3.4 parts 710T (IPA decentralized titanium oxide dispersion liquid, TAYCA CORPORATION makes), thereby obtain organosiloxane resins coating (ii-11).
[reference example IV-13]
Behind the 1M hydrochloric acid of 1 part of adding in 133 parts the water-dispersion type cataloid dispersion liquids (カ タ ロ イ De SN-35, solid component concentration 30 weight %, catalyst change into industry (strain) manufacturing), fully stir.This dispersion liquid is cooled to 10 ℃, at the ice-water bath cooling mix reagent of the dimethyldimethoxysil,ne of 208.8 parts of MTMSs of dropping and 4.7 parts down.After dripping end; Stirred 10 hours down at 30 ℃; Then to wherein mixing 1.1 parts of choline methanol solutions (content of choline is 45 weight %), 6.7 parts acetic acid and 210 parts isopropyl alcohol as retarder thinner as curing catalysts; Further add 6.7 parts 710T, thereby obtain organosiloxane resins coating (ii-12).
Figure S2007800017034D00901
In table 14, the material that each symbolic representation is identical with table 10.
(making and the evaluation of formed body (duplexer))
Carry out the evaluation of formed body with following method.In addition, then adopt the evaluation method identical to carry out to outward appearance, connecting airtight property and hot water resistance with above-mentioned [I].Wherein, hot water resistance is a dipping 3 hours and estimate in boiled water.
Mar proof: according to JIS K6735; CS-10F (TYPE IV) wear ring with Calibrase society system; Carry out 500 times Taber wear test with bear a heavy burden one side in two finishing coats of 500g; The haze value after the mensuration Taber wear test and the poor Δ H of the haze value before the Taber wear test, and estimate.
Weatherability: as ultraviolet shadow surface, with SUGA TESTINSTRUMENTS CO., the Super Xenon Weather Meter SX-75 that LTD makes is with UV exposure intensity 180W/m with the one side of test piece 2, in 63 ℃, 120 minutes of the blackboard temperatures 18 minutes be under the condition of raining, carry out 3000 hours exposure test, take out test piece, the outward appearance after the evaluation test, connecting airtight property.
[EXAMPLE IV-1]
Use dip coating; The acrylic resin paint (i-28) that will be obtained by reference example IV-7 is coated on two surfaces of the thick PC resin sheeting of 5mm, so that the thickness after the heat cure becomes 8 μ m; And after leaving standstill 20 minutes under 25 ℃, under 130 ℃, carry out 1 hour heat cure.Then; On the tunicle surface of this thin plate; Be coated with the organosiloxane resins composition (ii-11) that obtains by reference example IV-12 with dip coating, so that the thickness after the heat cure becomes 4 μ m, and after leaving standstill 20 minutes under 25 ℃; Under 125 ℃, carry out 1 hour heat cure, obtain PC resin-formed body (duplexer).The formation and the evaluation result of resulting PC laminated resin body are shown in Table 15.
[EXAMPLE IV-2]
Use dip coating; The acrylic resin paint (i-29) that will be obtained by reference example IV-8 is coated on two surfaces of the thick PC resin sheeting of 5mm, so that the thickness after the heat cure becomes 8 μ m; And after leaving standstill 20 minutes under 25 ℃, under 130 ℃, carry out 1 hour heat cure.Then; On the tunicle surface of this thin plate; Be coated with the organosiloxane resins composition (ii-11) that obtains by reference example IV-12 with dip coating, so that the thickness after the heat cure becomes 4 μ m, and after leaving standstill 20 minutes under 25 ℃; Under 125 ℃, carry out 1 hour heat cure, obtain PC resin-formed body (duplexer).The formation and the evaluation result of resulting PC laminated resin body are shown in Table 15.
[EXAMPLE IV-3]
Use dip coating; The acrylic resin paint (i-29) that will be obtained by reference example IV-8 is coated on two surfaces of the thick PC resin sheeting of 5mm, so that the thickness after the heat cure becomes 10 μ m; And after leaving standstill 20 minutes under 25 ℃, under 130 ℃, carry out 1 hour heat cure.Then; On the tunicle surface of this thin plate; Be coated with the organosiloxane resins composition (ii-12) that obtains by reference example IV-13 with dip coating, so that the thickness after the heat cure becomes 5 μ m, and after leaving standstill 20 minutes under 25 ℃; Under 125 ℃, carry out 1 hour heat cure, obtain PC resin-formed body (duplexer).The formation and the evaluation result of resulting PC laminated resin body are shown in Table 15.
[EXAMPLE IV-4]
Use dip coating; The acrylic resin paint (i-30) that will be obtained by reference example IV-9 is coated on two surfaces of the thick PC resin sheeting of 5mm, so that the thickness after the heat cure becomes 8 μ m; And after leaving standstill 20 minutes under 25 ℃, under 130 ℃, carry out 1 hour heat cure.Then; On the tunicle surface of this thin plate; Be coated with the organosiloxane resins composition (ii-12) that obtains by reference example IV-13 with dip coating, so that the thickness after the heat cure becomes 5 μ m, and after leaving standstill 20 minutes under 25 ℃; Under 125 ℃, carry out 1 hour heat cure, obtain PC resin-formed body (duplexer).The formation and the evaluation result of resulting PC laminated resin body are shown in Table 15.
[EXAMPLE IV-5]
Use dip coating; The acrylic resin paint (i-31) that will be obtained by reference example IV-10 is coated on two surfaces of the thick PC resin sheeting of 5mm, so that the thickness after the heat cure becomes 8 μ m; And after leaving standstill 20 minutes under 25 ℃, under 130 ℃, carry out 1 hour heat cure.Then; On the tunicle surface of this thin plate; Be coated with the organosiloxane resins coating (ii-11) that obtains by reference example IV-12 with dip coating, so that the thickness after the heat cure becomes 4 μ m, and after leaving standstill 20 minutes under 25 ℃; Under 125 ℃, carry out 1 hour heat cure, obtain PC resin-formed body (duplexer).The formation and the evaluation result of resulting PC laminated resin body are shown in Table 15.
[Comparative Example I V-1]
Use dip coating; The acrylic resin paint (i-32) that will be obtained by reference example IV-11 is coated on two surfaces of the thick PC resin sheeting of 5mm, so that the thickness after the heat cure becomes 8 μ m; And after leaving standstill 20 minutes under 25 ℃, under 130 ℃, carry out 1 hour heat cure.Then; On the tunicle surface of this thin plate; Be coated with the organosiloxane resins composition (ii-11) that obtains by reference example IV-12 with dip coating, so that the thickness after the heat cure becomes 4 μ m, and after leaving standstill 20 minutes under 25 ℃; Under 125 ℃, carry out 1 hour heat cure, obtain PC resin-formed body (duplexer).The formation and the evaluation result of resulting PC laminated resin body are shown in Table 15.
Figure S2007800017034D00941

Claims (22)

1. duplexer; This duplexer comprises base material, make the ground floor that the acrylic acid resin composition heat cure forms and the second layer that the organosiloxane resins composition heat cured is formed; And the order according to base material, ground floor and the second layer forms, and it is characterized in that
Said acrylic acid resin composition comprises: (A) acrylic copolymer, and it contains the repetitive with following formula (A) expression of at least 70 moles of %; (B) block polyisocyanate compound, it has the ratio that is converted into NCO of 5.5～50 weight %, and with respect to the hydroxyl in the acrylic copolymer of the formula (A) of 1 equivalent, has the NCO of 0.8～1.5 equivalent; (C) curing catalysts, it is 0.001～0.4 weight portion with respect to (A) composition of 100 weight portions and (B) total amount of composition; And (D) triazines ultra-violet absorber; Its with respect to (A) composition of 100 weight portions and (B) total amount of composition be 0～40 weight portion, and with following formula (D) expression, wherein; Triazines ultra-violet absorber residue in the formula (A) is 1～40 weight % with (D) total content of composition
In the formula (A), X is hydrogen atom or methyl; Y is that methyl, ethyl, cycloalkyl, carbon number are 2～5 hydroxy alkyl or triazines ultra-violet absorber residue; And the ratio of hydrogen atom is 30 moles below the % among the X, and the ratio of cycloalkyl is that the ratio of 1～85 mole of %, triazines ultra-violet absorber residue is that the ratio of 0～15 mole of %, ethyl is 1～98 mole of % among the Y,
Figure FSB00000245176800012
In the formula (D), R 4The expression carbon number is 1～18 alkyl, with-CH 2CH (OH) CH 2O-R 8The substituting group of expression or with-CH (CH 3) C (O) O-R 9The substituting group of expression, wherein, R 8Be that carbon number is 1～18 alkyl, R 9Be that carbon number is 1～18 alkyl; R 5Expression hydrogen atom, carbon number are that 1～18 alkyl or carbon number are 1～18 alkoxyl, R 6, R 7Represent independently that respectively hydrogen atom, carbon number are that 1～18 alkyl, carbon number are 1～18 alkoxyl or phenyl, this phenyl is that 1～18 alkyl or halogen atom replace or be not substituted by carbon number; V representes that hydrogen atom, OH base or carbon number are 1～12 alkyl;
Said organosiloxane resins composition comprises: (E) cataloid; (F) hydrolytic condensate of alkoxy silane, it is represented with following formula (F); And (G) metal oxide, wherein, (E) content of composition is 10～60 weight %, (F) content of composition is converted into R 1 mR 2 nSiO (4-m-n)/2Be 40～90 weight %, with respect to (E) composition of 100 weight portions and (F) total amount of composition, (G) composition is 0～15 weight portion,
R 1 mR 2 nSi(OR 3) 4-m-n (F)
In the formula (F), R 1, R 2Represent independently that respectively carbon number is that 1～4 alkyl, vinyl or carbon number are 1～3 alkyl; This carbon number is 1～3 the selected free methyl acryloxy of alkyl, amino, glycidoxy and 3, and an above group in the group that the 4-epoxycyclohexyl is formed replaces; R 3Be the alkyl or the vinyl of carbon number 1～4, m, n represent the arbitrary integer in 0,1,2 respectively independently, and m+n is the arbitrary integer in 0,1,2.
2. duplexer as claimed in claim 1; It is characterized in that; (A) acrylic copolymer contains the repetitive with following formula (A-3) expression of the repetitive with following formula (A-2) expression of the repetitive with following formula (A-1) expression of 1～98 mole of %, 1～85 mole of %, 1～15 mole of %, the repetitive with following formula (A-4) expression of 0～15 mole of %; And their total amount is at least 70 moles of %; And the triazines ultra-violet absorber residue in the formula (A-4) is 1～40 weight % with (D) total content of composition
Figure FSB00000245176800021
Figure FSB00000245176800031
In the formula, Y 1Be methyl or ethyl, Y 2Be cycloalkyl, X 1Be hydrogen atom or methyl, X 2Be hydrogen atom or methyl, Y 3Be the alkylidene of carbon number 2～5, Y 4Be triazines ultra-violet absorber residue, X 3Be hydrogen atom or methyl.
3. duplexer as claimed in claim 2 is characterized in that, the content of the repetitive of usefulness formula (A-4) expression of acrylic copolymer is 0 mole of %; And with respect to (A) composition of 100 weight portions and (B) total amount of composition, (D) content of composition is 1～40 weight portion.
4. duplexer as claimed in claim 2 is characterized in that, with respect to (A) composition of 100 weight portions and (B) total amount of composition, (D) content of composition is 0 weight portion; And the content of the repetitive of the usefulness formula (A-4) of acrylic copolymer expression is 0.1～15 mole of %.
5. duplexer as claimed in claim 2; It is characterized in that; In the acrylic copolymer, the total content of the repetitive of the repetitive of the repetitive of formula (A-2) expression of the repetitive of the formula of 50～98 moles of % (A-1) expression, 1～35 mole of %, formula (A-3) expression of 1～15 mole of % and formula (A-4) expression of 0～10 mole of % is at least 70 moles of %.
6. duplexer as claimed in claim 2; It is characterized in that; Acrylic copolymer contains the repetitive of representing with following formula (A-5) of repetitive and 0.1～10 mole of % of formula (A-4) expression of the repetitive of formula (A-3) expression of the repetitive of formula (A-2) expression of the repetitive of formula (A-1) expression of 50～97.9 moles of %, 1～35 mole of %, 1～15 mole of %, 0～10 mole of %; And; In the repetitive total amount with respect to the acrylic copolymer of 100 moles of %, (A-1)～(A-5) total amount of unit is at least 70 moles of %
Figure FSB00000245176800041
In the formula (A-5), R 10The alkyl or the alkoxyl of expression hydrogen atom, carbon number 1～14.
7. duplexer as claimed in claim 2; It is characterized in that; In the acrylic copolymer, the total content of the repetitive of the repetitive of formula (A-3) expression of the repetitive of the formula of 1～60 mole of % (A-1) expression, the repetitive that surpasses formula (A-2) expression below 35 moles of % and the 85 moles of %, 1～15 mole of % and formula (A-4) expression of 0.1～15 mole of % is at least 70 moles of %.
8. duplexer as claimed in claim 2; It is characterized in that; Acrylic copolymer contains the repetitive of representing with following formula (A-5) of repetitive and 0.1～20 mole of % of formula (A-4) expression of the repetitive of formula (A-3) expression of the repetitive of formula (A-1) expression of 1～59.9 mole of %, the repetitive that surpasses formula (A-2) expression below 35 moles of % and the 85 moles of %, 1～15 mole of %, 0.1～10 mole of %; And; In the repetitive total amount with respect to the acrylic copolymer of 100 moles of %, (A-1)～(A-5) total amount of unit is at least 70 moles of %
Figure FSB00000245176800042
In the formula (A-5), R 10The alkyl or the alkoxyl of expression hydrogen atom, carbon number 1～14.
9. duplexer as claimed in claim 1 is characterized in that, (C) composition is at least a compound that is selected from the group of being made up of organo-tin compound, organic titanic compound, organic zirconate, tertiary amine compound, quarternary ammonium salt compound.
10. duplexer as claimed in claim 1 is characterized in that, with respect to (E) composition of 100 weight portions and (F) total amount of composition, (G) content of composition is 0.1～15 weight portion.
11. duplexer as claimed in claim 1 is characterized in that, (G) composition is at least a metal oxide that is selected from the group of being made up of titanium oxide, zinc oxide, cerium oxide, tin oxide and tungsten oxide.
12. duplexer as claimed in claim 1 is characterized in that, base material is a polycarbonate resin.
13. a glass pane, it is to be formed by any one described duplexer in the claim 1～12.
14. an acrylic acid resin composition is characterized in that, comprising:
(A) acrylic copolymer; It contains the repetitive of representing with following formula (A-4) of the repetitive of representing with following formula (A-3) and 0～15 mole of % of the repetitive with following formula (A-2) expression of the repetitive with following formula (A-1) expression of 1～98 mole of %, 1～85 mole of %, 1～15 mole of %, and their total amount is at least 70 moles of %;
(B) block polyisocyanate compound, it has the ratio that is converted into NCO of 5.5～50 weight %, and with respect to the hydroxyl in the acrylic copolymer of 1 equivalent, has the NCO of 0.8～1.5 equivalent;
(C) curing catalysts, its with respect to (A) composition of 100 weight portions and (B) total amount of composition be 0.001～0.4 weight portion; And,
(D) triazines ultra-violet absorber, its with respect to (A) composition of 100 weight portions and (B) total amount of composition be 0～40 weight portion, and with following formula (D) expression,
Wherein, the triazines ultra-violet absorber residue in the formula (A-4) is 1～40 weight % with (D) total content of composition,
Figure FSB00000245176800051
Figure FSB00000245176800061
In the formula, Y 1Be methyl or ethyl, Y 2Be cycloalkyl, X 1Be hydrogen atom or methyl, X 2Be hydrogen atom or methyl, Y 3Be the alkylidene of carbon number 2～5, Y 4Be triazines ultra-violet absorber residue, X 3Be hydrogen atom or methyl;
Figure FSB00000245176800062
In the formula (D), R 4The expression carbon number is 1～18 alkyl, with-CH 2CH (OH) CH 2O-R 8The substituting group of expression or with-CH (CH 3) C (O) O-R 9The substituting group of expression, wherein, R 8Be that carbon number is 1～18 alkyl, R 9Be that carbon number is 1～18 alkyl; R 5Expression hydrogen atom, carbon number are that 1～18 alkyl or carbon number are 1～18 alkoxyl; R 6, R 7Represent independently that respectively hydrogen atom, carbon number are that 1～18 alkyl, carbon number are 1～18 alkoxyl or phenyl, this phenyl is that 1～18 alkyl or halogen atom replace or be not substituted by carbon number; V representes that hydrogen atom, OH base or carbon number are 1～12 alkyl.
15. acrylic acid resin composition as claimed in claim 14 is characterized in that, the content of the repetitive of usefulness formula (A-4) expression of acrylic copolymer is 0 mole of %; And with respect to (A) composition of 100 weight portions and (B) total amount of composition, (D) content of composition is 1～40 weight portion.
16. acrylic acid resin composition as claimed in claim 14 is characterized in that, with respect to (A) composition of 100 weight portions and (B) total amount of composition, (D) content of composition is 0 weight portion; And the content of the repetitive of the usefulness formula (A-4) of acrylic copolymer expression is 0.1～15 mole of %.
17. acrylic acid resin composition as claimed in claim 14; It is characterized in that; In the acrylic copolymer, the total content of the repetitive of the repetitive of the repetitive of formula (A-2) expression of the repetitive of the formula of 50～98 moles of % (A-1) expression, 1～35 mole of %, formula (A-3) expression of 1～15 mole of % and formula (A-4) expression of 0～10 mole of % is at least 70 moles of %.
18. like the said acrylic acid resin composition of claim 14; It is characterized in that; Acrylic copolymer contains the repetitive of representing with following formula (A-5) of repetitive and 0.1～10 mole of % of formula (A-4) expression of the repetitive of formula (A-3) expression of the repetitive of formula (A-2) expression of the repetitive of formula (A-1) expression of 50～97.9 moles of %, 1～35 mole of %, 1～15 mole of %, 0～10 mole of %; And; With respect to the repetitive total amount of the acrylic copolymer of 100 moles of %, (A-1)～(A-5) total amount of unit is at least 70 moles of %
Figure FSB00000245176800071
In the formula (A-5), R 10The alkyl or the alkoxyl of expression hydrogen atom, carbon number 1～14.
19. acrylic acid resin composition as claimed in claim 14; It is characterized in that; In the acrylic copolymer, the total content of the repetitive of the repetitive of formula (A-3) expression of the repetitive of the formula of 1～60 mole of % (A-1) expression, the repetitive that surpasses formula (A-2) expression below 35 moles of % and the 85 moles of %, 1～15 mole of % and formula (A-4) expression of 0.1～15 mole of % is at least 70 moles of %.
20. acrylic acid resin composition as claimed in claim 14; It is characterized in that; Acrylic copolymer contains the repetitive of representing with following formula (A-5) of repetitive and 0.1～20 mole of % of formula (A-4) expression of the repetitive of formula (A-3) expression of the repetitive of formula (A-1) expression of 1～59.9 mole of %, the repetitive that surpasses formula (A-2) expression below 35 moles of % and the 85 moles of %, 1～15 mole of %, 0.1～10 mole of %; And; In the repetitive total amount with respect to the acrylic copolymer of 100 moles of %, (A-1)～(A-5) total amount of unit is at least 70 moles of %
Figure FSB00000245176800081
In the formula (A-5), R 10The alkyl or the alkoxyl of expression hydrogen atom, carbon number 1～14.
21. acrylic acid resin composition as claimed in claim 14; It is characterized in that (C) composition is at least a compound that is selected from the group of being made up of organo-tin compound, organic titanic compound, organic zirconate, tertiary amine compound and quarternary ammonium salt compound.
22. acrylic acid resin composition as claimed in claim 14 is characterized in that, also contains solvent, and resin concentration is 1～50 weight %.
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